钒改性锂离子电池正极材料LiFe0.5Mn0.5PO4/C 电化学性能

引用本文: 龚强, 王红, 廖小珍, 麻微, 何雨石, 马紫峰. 钒改性锂离子电池正极材料LiFe_0.5Mn_0.5PO₄/C 电化学性能[J]. 物理化学学报, 2012, 28(01): 100-104. doi: 10.3866/PKU.WHXB201228100 shu

Citation: NG Qiang, WANG Hong, LIAO Xiao-Zhen, MA Wei, HE Yu-Shi, MA Zi-Feng. Electrochemical Performance of Vanadium Modified LiFe_0.5Mn_0.5PO₄/C Cathode Materials for Lithium-Ion Batteries[J]. Acta Physico-Chimica Sinica, 2012, 28(01): 100-104. doi: 10.3866/PKU.WHXB201228100 shu

钒改性锂离子电池正极材料LiFe_0.5Mn_0.5PO₄/C 电化学性能

基金项目:
国家自然科学基金(21073120, 20773087, 21006063) (21073120, 20773087, 21006063)

上海市科学技术委员会科技支撑项目(09DZ1203603, 10DZ1202702)资助项目 (09DZ1203603, 10DZ1202702)

摘要: 采用高温固相反应, 以NH₄VO₃为钒源合成了化学计量式为(1-x)LiFe_0.5Mn_0.5PO₄-xLi₃V₂(PO₄)₃/C (x=0,0.1, 0.2, 0.25, 1)的钒改性磷酸锰铁锂正极材料. 电化学测试表明钒改性能明显提高磷酸锰铁锂材料的充放电性能, 其中x=0.2 时得到的0.8LiFe_0.5Mn_0.5PO₄-0.2Li₃V₂(PO₄)₃/C(标记为LFMP-LVP/C)材料电化学性能最好, 其0.1C倍率时的放电比容量为141 mAh·g^-1. X射线衍射(XRD)分析指出LFMP-LVP/C材料的微观结构为橄榄石型LiFe_0.5Mn_0.5PO₄/C 和NASICON型Li₃V₂(PO₄)₃组成的双相结构. 能量色射X射线谱(EDS)分析结果指出, Fe、Mn、V、P元素在所合成材料中的分布非常均匀, 表明所制备材料成分的均一性. Li₃V₂(PO₄)₃改性使材料的电导率明显提高. LiFe_0.5Mn_0.5PO₄的电导率为1.9×10^-8 S·cm^-1, 而LFMP-LVP材料电导率提高到2.7×10^-7 S·cm^-1.与纯Li₃V₂(PO₄)₃的电导率(2.3×10^-7 S·cm^-1)相近. 电化学测试表明钒改性使LFMP-LVP/C材料充放电过程电极极化明显减小, 从而电化学性能得到显著提高. 本文工作表明Li₃V₂(PO₄)₃改性可成为提高橄榄石型磷酸盐锂离子电池正极材料电化学性能的一种有效方法.

关键词:

English

Electrochemical Performance of Vanadium Modified LiFe_0.5Mn_0.5PO₄/C Cathode Materials for Lithium-Ion Batteries

1.
Institute of Electrochemical and Energy Technology, Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China
Received Date: 20 July 2011
Available Online: 29 December 2011
Fund Project:
国家自然科学基金(21073120, 20773087, 21006063)

上海市科学技术委员会科技支撑项目(09DZ1203603, 10DZ1202702)资助项目

Abstract: Vanadium modified LiFe_0.5Mn_0.5PO₄/C cathode materials with a nominal composition of (1-x)LiFe_0.5Mn_0.5PO₄-xLi₃V₂(PO₄)₃/C (x=0, 0.1, 0.2, 0.25, 1) were prepared by a solid-state reaction using NH4VO3 as the vanadium source. The electrochemical performance of the LiFe_0.5Mn_0.5PO₄-based compounds improved upon vanadium modification. The 0.8LiFe_0.5Mn_0.5PO₄-0.2Li₃V₂(PO₄)₃/C (LFMP-LVP/C) sample exhibited the highest discharge capacity of 141 mAh·g^-1 at 0.1C rate. X-ray diffraction analyses revealed a dual phase of the LFMP-LVP/C composite with the coexistence of an olivine-type LiFe_0.5Mn_0.5PO₄/C phase and a NASICON-type Li₃V₂(PO₄)₃ phase. Energy dispersive X-ray spectroscopy (EDS) analysis indicates a uniform distribution of Fe, Mn, V, and P in the composite. The electronic conductivity of LFMP-LVP was found to be 2.7×10^-7 S·cm^-1, which is much higher than the value (1.9×10^-8 S·cm^-1) of LiFe_0.5Mn_0.5PO₄ and similar to the value (2.3 × 10^-7 S·cm^-1) of pure Li₃V₂(PO₄)₃. Vanadium modification remarkably reduced the electrode polarization of the LFMP-LVP/C cathode during the charge-discharge procedure. This suggests that vanadium modification is an effective method to improve the electrochemical performance of olivine-type cathode materials.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

钒改性锂离子电池正极材料LiFe_0.5Mn_0.5PO₄/C 电化学性能

English

Electrochemical Performance of Vanadium Modified LiFe_0.5Mn_0.5PO₄/C Cathode Materials for Lithium-Ion Batteries

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