Surface Modification of Li-rich Layered Li(Li0.17Ni0.2Mn0.58Co0.05)O2 Oxide with TiO2(B) as the Cathode for Lithium-ion Batteries

doi:10.15541/jim20140047

Abstract

Abstract:

The Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide was prepared by a spray-drying method. Subsequently, the surface modification with TiO₂(B) nanocrystallites (2wt%, 4wt%, 6wt%, 8wt%) was introduced into the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide by precipitation method. It is demonstrated that there is no obvious change in the crystallographic structure of the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide based on the analysis of XRD, SEM and TEM, while only the surface of the oxide is modified with TiO₂(B) nanocrystallites. It is indicated from DSC curves that the thermal stability of Li-rich layered oxide is obviously improved by the surface modification with TiO₂(B) nanocrystallites. Correspondingly, the large discharge capacity of 296.4 mAh/g and high coulombic efficiency of 84.5% are obtained at 0.1C rate (1C=300 mA/g) in the first cycle for the Li-rich layered oxide after the surface modification with TiO₂(B) nanocrystallites (4wt%). Moreover, the capacity retention after 100 cycles is increased from 69.5% for the pristine sample to 80.2% for the TiO₂(B)-modified sample. Even at 2C rate, the large discharge capacity of 166.5 mAh/g is still obtained for the TiO₂(B)-modified sample. Apparently, it is demonstrated from the above results that the surface modification with TiO₂(B) nanocrystallites can improve the thermal stability and electrochemical performance of the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide.

null

Key words: lithium ion battery, cathode, Li-rich layered oxide, surface modification, TiO2(B)

CLC Number:

TM912

LIU Qin, YUAN Wen, GAO Xue-Ping. Surface Modification of Li-rich Layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂Oxide with TiO₂(B) as the Cathode for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2014, 29(12): 1257-1264.

Figures/Tables 10

Fig. 1 XRD patterns of as-prepared sample (a) and the samples (b-e) modified with different TiO2(B) contents

Fig. 2 SEM images of samples modified with different TiO2(B) contents (a)As-prepared; (b) 2wt%; (c) 4wt%; (d) 6wt%; (e) 8wt%

Fig. 3 TEM images of as-prepared sample (a) and the sample modified with 4wt% TiO2(B) (b)

Fig. 4 DSC profiles of the samples modified with different TiO2(B) contents after charging to 4.8 V (vs Li/Li+)

Fig. 5 Cyclic voltammorgrams of the as-prepared sample (a) and the sample modified with 4wt% TiO2(B) (b) at scan rate of 0.1 mV/s

Fig. 6 Initial charge curves and subsequent discharge curves of the as-prepared sample (a) and the sample modified with 4wt% TiO2 (B) (b) at different cycles (0.1C rate)

Fig. 7 Cycle performance of the samples modified with different TiO2(B) contents at 0.1C rate

Table. 1 Electrochemical data of TiO2(B)-modified samples in the first cycle (0.1C rate)

TiO₂(B) content	Initial charge capacity / (mAh·g^-1)	Initial discharge capacity / (mAh·g^-1)	Initial irreversible capacity loss / (mAh·g^-1)	Initial coulombic efficiency	Capacity retention after 100 cycles
0	384.2	298.7	85.5	77.7%	69.5%
2wt%	347.7	286.5	61.2	82.4%	79.1%
4wt%	351.7	296.4	55.3	84.3%	80.2%
6wt%	333.6	263.6	70.1	79.0%	78.9%
8wt%	326.0	255.9	106.1	78.5%	78.0%

Fig. 8 Cycle performance of the samples modified with different TiO2(B) contents at 1C rates

Fig. 9 Rate capability of and the samples modified with different TiO2(B) contents at varied rates

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Surface Modification of Li-rich Layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂Oxide with TiO₂(B) as the Cathode for Lithium-ion Batteries

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