Preparation of Li1.2Mn0.54Co0.13Ni0.13O2@V2O5 Core-shell Composite and Its Electrochemical Properties

doi:10.3724/SP.J.1077.2014.13322

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 10

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

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

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)

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

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

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

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

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

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

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

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