Li3V2(PO4)3/C正极材料在不同电压区间的电化学行为及容量衰减原因

doi:10.3866/PKU.WHXB201412172

Abstract

Abstract:

Li₃V₂(PO₄)₃/C cathode material was synthesized by the sol-gel method. The electrochemical properties of the sample in different voltage ranges (3.0-4.5 V and 3.0-4.8 V) were investigated by galvanostatic charge/discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Results show that the cycling performance and rate capability of Li₃V₂(PO₄)₃/C in voltage range of 3.0-4.8 V are worse than those in voltage range of 3.0-4.5 V. The initial specific discharge capacity in voltage range of 3.0-4.5 V at 0.1C rate (1C=150 mA·g^-1) is 127.0 mAh·g^-1, and 99.5% of the initial capacity was maintained after 50 cycles in contrast to 168.2 mAh·g^-1 and 78.5% in voltage range of 3.0-4.8 V. The discharge capacities in voltage ranges of 3.0-4.5 V and 3.0-4.8 V are 99.0% and 80.7% of the initial 0.1C rate respectively when the charge/discharge rate recovered to 0.1C rate after the high rate test. Part of the third lithium ion may be extracted at less than 4.5 V after several cycles in voltage range of 3.0-4.8 V with a capacity increase of 7.4%. CV results indicate that the irreversible capacity fading between 3.0 and 4.8 V may be attributed to irreversible behavior of the first lithium ion. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results show that the structure of Li₃V₂(PO₄)₃ changes slightly after operating between 3.0 and 4.8 V. Inductively coupled plasma (ICP) results indicate the presence of dissolved V in the cycled electrolytes. The structural distortion and the V dissolved in the electrolyte may be the main reasons for the decrease in capacity.

Key words: Li₃V₂(PO₄)₃/C, Electrochemical behavior, Voltage range, Capacity fading

TANG Yan, ZHONG Yan-Jun, OU Qing-Zhu, LIU Heng, ZHONG Ben-He, GUO Xiao-Dong, WANG Xin-Long. Electrochemical Behavior and Reasons for the Decrease in Capacity of the Li₃V₂(PO₄)₃/C Cathode Material in Different Voltage Ranges[J].Acta Phys. -Chim. Sin., 2015, 31(2): 277-284.

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Electrochemical Behavior and Reasons for the Decrease in Capacity of the Li₃V₂(PO₄)₃/C Cathode Material in Different Voltage Ranges

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Electrochemical Behavior and Reasons for the Decrease in Capacity of the Li₃V₂(PO₄)₃/C Cathode Material in Different Voltage Ranges