Preparation and Electrochemical Properties of Li₃V₂(PO₄)3-xBrx/Carbon Composites as Cathode Materials for Lithium-Ion Batteries

Xiaoyu Cao; Lulu Mo; Limin Zhu; Lingling Xie

doi:10.3390/nano7030052

Preparation and Electrochemical Properties of Li₃V₂(PO₄)_3-xBr_x/Carbon Composites as Cathode Materials for Lithium-Ion Batteries

Nanomaterials (Basel). 2017 Feb 24;7(3):52. doi: 10.3390/nano7030052.

Authors

Xiaoyu Cao^{1

2}, Lulu Mo^{3

4}, Limin Zhu^{5

6}, Lingling Xie^{7

8}

Affiliations

¹ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China. caoxy@haut.edu.cn.
² Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China. caoxy@haut.edu.cn.
³ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China. molulu_1989@126.com.
⁴ Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China. molulu_1989@126.com.
⁵ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China. lmzhu@haut.edu.cn.
⁶ Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China. lmzhu@haut.edu.cn.
⁷ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China. linglingxie51@163.com.
⁸ Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou City, Henan University of Technology, Zhengzhou 450001, China. linglingxie51@163.com.

Abstract

Li₃V₂(PO₄)_3-xBr_x/carbon (x = 0.08, 0.14, 0.20, and 0.26) composites as cathode materials for lithium-ion batteries were prepared through partially substituting PO₄^3- with Br^-, via a rheological phase reaction method. The crystal structure and morphology of the as-prepared composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and electrochemical properties were evaluated by charge/discharge cycling and electrochemical impedance spectroscopy (EIS). XRD results reveal that the Li₃V₂(PO₄)_3-xBr_x/carbon composites with solid solution phase are well crystallized and have the same monoclinic structure as the pristine Li₃V₂(PO₄)₃/carbon composite. It is indicated by SEM images that the Li₃V₂(PO₄)_3-xBr_x/carbon composites possess large and irregular particles, with an increasing Br^- content. Among the Li₃V₂(PO₄)_3-xBr_x/carbon composites, the Li₃V₂(PO₄)_2.86Br_0.14/carbon composite shows the highest initial discharge capacity of 178.33 mAh·g^-1 at the current rate of 30 mA·g^-1 in the voltage range of 4.8-3.0 V, and the discharge capacity of 139.66 mAh·g^-1 remains after 100 charge/discharge cycles. Even if operated at the current rate of 90 mA·g^-1, Li₃V₂(PO₄)_2.86Br_0.14/carbon composite still releases the initial discharge capacity of 156.57 mAh·g^-1, and the discharge capacity of 123.3 mAh·g^-1 can be maintained after the same number of cycles, which is beyond the discharge capacity and cycleability of the pristine Li₃V₂(PO₄)₃/carbon composite. EIS results imply that the Li₃V₂(PO₄)_2.86Br_0.14/carbon composite demonstrates a decreased charge transfer resistance and preserves a good interfacial compatibility between solid electrode and electrolyte solution, compared with the pristine Li₃V₂(PO₄)₃/carbon composite upon cycling.

Keywords: Li3V2(PO4)3/carbon composites; bromine ion doping; cathode materials; enhanced electrochemical performances; lithium-ion batteries.