Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料的制备及其电化学性能

doi:10.3724/SP.J.1077.2014.13322

摘要/Abstract

摘要：

采用溶胶-凝胶技术在富锂锰基固溶体Li_1.2Mn_0.54Co_0.13Ni_0.13O₂表面包覆V₂O₅, 制备了Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅核壳复合材料。通过扫描电镜(SEM)和透射电镜(TEM)观察其形貌, X射线衍射(XRD)分析确定其结构。结果显示, 结晶态的V₂O₅均匀包覆在类球形Li_1.2Mn_0.54Co_0.13Ni_0.13O₂颗粒表面, Li_1.2Mn_0.54Co_0.13Ni_0.13O₂材料的晶体结构在包覆前后保持不变。X射线光电子能谱(XPS)分析结果表明, 该核壳复合材料首次充电时, 锂离子嵌入V₂O₅包覆层。电化学测试结果表明, 表面包覆15%V₂O₅的核壳复合材料具有最佳的电化学性能: 0.1C倍率下放电比容量为276 mAh/g, 首次充放电库仑效率达到94%, 50次循环后容量保持率达89%。

关键词: 富锂锰基固溶体, 表面包覆, 核壳结构, 库仑效率, 锂离子电池

Abstract:

Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅ core-shell composite was prepared by coating V₂O₅ on the surface of the lithium-rich manganese-based solid solution Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ particles through Sol-Gel technology. Its morphology was observed by using scanning electronic microscope (SEM) and transition electronic microscope (TEM) while the crystal structure was calculated from the results of the X-ray diffraction (XRD). It is found that the quasi spherical core-shell composite is coated homogeneously with the crystalline V₂O₅ nanoparticles. The crystal structure of Li_1.2Mn_0.54Co_0.13Ni_0.13O₂core is maintained after the surface coating. XPS spectra suggest that Li⁺ ions intercalate the crystal structure of the V₂O₅ shell during the first charge. The electrochemical measurements show that the core-shell composite being coated with 15% V₂O₅ could deliver an initial capacity of 276 mAh/g at the rate of 0.1C accompamied by a coulombic efficiency of 94%. It can remain 89% of the initial capacity after 50 charge/discharge cycles.

Key words: Li-rich manganese-based solid solution, surface coating, core-shell structure, coulombic efficiency, lithium-ion battery

中图分类号:

TQ174

聂文波, 肖其昌, 王京亮, 雷钢铁, 肖启振, 李朝晖. Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅核壳复合材料的制备及其电化学性能[J]. 无机材料学报, 2014, 29(3): 257-263.

NIE Wen-Bo, XIAO Qi-Chang, WANG Jing-Liang, LEI Gang-Tie, XIAO Qi-Zhen, LI Zhao-Hui. Preparation of Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅ Core-shell Composite and Its Electrochemical Properties[J]. Journal of Inorganic Materials, 2014, 29(3): 257-263.

图/表 10

图 1 V2O5、Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料(LMS3)和Li1.2Mn0.54Co0.13Ni0.13O2(LMS0)的XRD图谱

Fig. 1 XRD patterns of V2O5, Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composite (LMS3) and Li1.2Mn0.54Co0.13Ni0.13O2 (LMS0)

图2 Li1.2Mn0.54Co0.13Ni0.13O2 (a)和Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料(b)的SEM照片

Fig. 2 SEM images of Li1.2Mn0.54Co0.13Ni0.13O2 (a) and Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composite

图 3 Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料TEM照片(a, b), 包覆层中V2O5的HRTEM照片(c)及其EDX图谱(d)

Fig. 3 TEM images of Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composite (a, b), HRTEM image of the V2O5 in the shell (c) and its EDX spectrum (d)

图4 Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料(LMS3)未充电(a)和首次充电至4.8 V后(b)的V2p2/3 XPS图谱, 及其首次充电至4.8 V后XRD图谱(c)

Fig. 4 XPS spectra of V2p2/3 in the Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composite (LMS3) before (a) and after (b) charged to 4.8 V in the first cycle, and their XRD patterns

图 5 样品LMS0(a)、LMS1(b)、LMS3(c)和V2O5(d)的循环伏安曲线

Fig. 5 Cyclic voltammograms of the samples LMS0 (a), LMS1 (b), LMS3 (c) and V2O5 (d)

图6 Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料的首次充放电曲线

Fig. 6 First charge/discharge profiles of the Li1.2Mn0.54Co0.13Ni0.13O2 @V2O5 core-shell composites Inset is local discharge curves of sample LMS3

表1 Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料的首次充放电参数过高温处理具有较高的结晶度, 因此, 所得的核壳复合材料具有优越的循环性能。

Table 1 First discharge/charge parameters of the Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composites in the first cycle

Mass fraction of the V₂O₅ in the composite/%	Initial charge capacity/(mAh·g^-1)	Initial discharge capacity/(mAh·g^-1)	Irreversible capacity/(mAh·g^-1)	Coulombic efficiency/%
0	354	259	95	73
5	339	266	73	78
10	323	272	51	84
15	292	276	16	94
20	278	279	-1	100

图 7 Li1.2Mn0.54Co0.13Ni0.13O2@V2O5核壳复合材料及V2O5的循环性能

Fig. 7 Cycling performances of the Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 core-shell composites and V2O5

图8 未包覆样品LMS0 (a)和包覆样品LMS3(b)在循环20次前后的Nyquist曲线

Fig. 8 Nyquist curves of the pristine (a) and the core-shell samples (b) before and after 20 cycles

表2 等效电路的阻抗参数

Table 2 Impedance parameters of the equipment circuit

Sample	R_s / Ω		R_ct / Ω
Sample	Before cycle	After 20 cycles	Before cycle	After 20 cycles
LMS0	3.94	4.02	21.6	133.0
LMS3	4.06	4.08	40.7	55.7

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Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅核壳复合材料的制备及其电化学性能

Preparation of Li_1.2Mn_0.54Co_0.13Ni_0.13O₂@V₂O₅ Core-shell Composite and Its Electrochemical Properties

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