锂离子电池正极材料Li1.2Mn0.54-xNi0.13Co0.13ZrxO2的制备及电化学性能

doi:10.3866/PKU.WHXB201406172

物理化学学报 >> 2014, Vol. 30 >> Issue (9): 1641-1649.doi: 10.3866/PKU.WHXB201406172

锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能

任祥忠, 刘涛, 孙灵娜, 张培新

深圳大学化学与化工学院, 广东深圳 518060

收稿日期:2014-04-18 修回日期:2014-06-16 发布日期:2014-08-29
通讯作者: 任祥忠 E-mail:renxz@szu.edu.cn
基金资助:
国家自然科学基金（21000174）及深圳市战略新兴产业发展基金（JCYJ20120613163733279，JCYJ20130329113849606）资助项目

Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries

REN Xiang-Zhong, LIU Tao, SUN Ling-Na, ZHANG Pei-Xin

College of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, P. R. China

Received:2014-04-18 Revised:2014-06-16 Published:2014-08-29
Contact: REN Xiang-Zhong E-mail:renxz@szu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (21000174), Shenzhen Strategic Emerging Industry Development Funds, China (JCYJ20120613163733279, JCYJ20130329113849606).

摘要/Abstract

摘要：

为了改善富锂锰基正极材料Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ 的循环性能，采用燃烧法合成了正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂（x=0.00，0.01，0.02，0.03，0.06）. 通过X射线衍射（XRD）和扫描电镜（SEM）对其结构与形貌进行了表征，利用恒电流充放电测试，循环伏安（CV）及电化学交流阻抗谱（EIS）技术对其电化学性能进行测试. 结果表明，Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂（x=0.00，0.01，0.02，0.03，0.06）正极材料均具有α-NaFeO₂型层状结构；在室温，2.0-4.8 V电压范围，以0.1C和1.0C（充放电电流以1.0C=180 mA·g^-1计算）倍率充放电进行测试，样品Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂的首次放电比容量分别为280.3 和206.4 mAh·g^-1. 其中，在1.0C倍率下，100次循环后容量保持率由原来的73.2%提高到88.9%；以5.0C倍率充放电进行测试，经50次循环后，掺杂正极材料的放电比容量为76.5 mAh·g^-1，而未掺杂材料仅有15.0 mAh·g^-1. 在50、25 和-10 ℃，2.0C倍率条件下，掺杂正极材料的电化学性能均得到有效改善，其中，在- 10℃ 经过50 次循环后正极材料Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂比未掺杂的正极材料相比，其放电比容量提高了61.1%.

关键词: 燃烧法, 锂离子电池, 正极材料, 富锂材料, 掺杂

Abstract:

To improve the cycling performance of lithium-rich cathode materials, Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ and Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ (x=0.00, 0.01, 0.02, 0.03, and 0.06) were synthesized by a combustion method. The structure and morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical performances were examined by cyclic voltammetry (CV), electrochemical AC impedance spectroscopy, and galvanostatic charge-discharge cycling. The results indicate that all of the doped samples have a layer of α-NaFeO₂. When charged and discharged at 0.1C and 1.0C (1.0C=180 mA·g^-1) in the voltage range of 2.0-4.8 V, the initial discharge capacities of Li_1.2Mn_0.52Ni_0.13Co_0.13Zr_0.02O₂ were 280.3 and 206.4 mAh·g^-1, respectively. Moreover, the capacity retention after 50 cycles improved from 73.2% to 88.9% at 1.0C at room temperature. Meanwhile, this system delivered a higher discharge capacity of 76.5 mAh·g^-1 than that of the bare materials (15 mAh·g^-1) at 5.0C after 50 cycles. Electrochemical performances of the doped samples were improved at a 2.0C rate at different temperatures (50, 25, and -10 ℃). Furthermore, compared with the undoped material, the specific discharge capacity increased by 61.1% at -10 ℃ after 50 cycles.

Key words: Combustion method, Lithium-ion battery, Cathode material, Lithium-rich material, Doping

MSC2000:

O646

任祥忠, 刘涛, 孙灵娜, 张培新. 锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能[J]. 物理化学学报, 2014, 30(9): 1641-1649.

REN Xiang-Zhong, LIU Tao, SUN Ling-Na, ZHANG Pei-Xin. Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2014, 30(9): 1641-1649.

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锂离子电池正极材料Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂的制备及电化学性能

Preparation and Electrochemical Performances of Li_1.2Mn_0.54-xNi_0.13Co_0.13Zr_xO₂ Cathode Materials for Lithium-Ion Batteries

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