Enhanced electrochemical properties of LiFe1-xMnxPO4/C composites synthesized from FePO4•2H2O nanocrystallites

被引:38
作者
Chen, Li [1 ]
Yuan, Yong-Qiang [1 ]
Feng, Xia [1 ]
Li, Ming-Wei [1 ]
机构
[1] Tianjin Univ, Dept Chem, Tianjin 300072, Peoples R China
关键词
Lithium-ion battery; Cathode material; Lithium manganese phosphate; Iron substitution; RECHARGEABLE LITHIUM BATTERIES; LIFEPO4/C CATHODE MATERIAL; PERFORMANCE; LIMNPO4; NANOCOMPOSITE; MECHANISM; PHOSPHATE; BEHAVIOR; SUCROSE; ROUTE;
D O I
10.1016/j.jpowsour.2012.04.089
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The high discharge potential of LiMnPO4, 4.1 V vs. Li/Li+, and its theoretical capacity of 170 mAh g(-1) make it a promising candidate as a cathode material in lithium-ion batteries. But extremely low electronics conductivity, slow lithium diffusion kinetics, and the Jahn-Teller effect of Mn3+ limit the electrochemical performances of LiMnPO4. In this work, the pre-synthesized and defined FePO4 center dot 2H(2)O nanocrystallites are used as one of the raw materials to synthesize LiFe1-xMnxPO4/C (x = 0.85, 0.75, 0.65) composites via solid-state reactions. The synthesized LiFe1-xMnxPO4 samples show well-crystallized structures and have enhanced electrochemical properties. There exist two plateaus around 3.5 and 4.1 V on both of their charge and discharge curves. Among the samples, the Fe0.25Mn0.75PO4 one exhibits the longest high-voltage charge/discharge plateau at 4.10 V/4.05 V, and has an average discharge voltage of similar to 3.78 V vs. Li/Li+ and a discharge capacity of similar to 130 mAh g(-1) at 0.05 C rate. For the Fe0.25Mn0.75PO4 sample, the noticeable improvement of its electrochemical performances is mainly attributed to iron substitution, the appropriate Mn/Fe ratio, and the well-ordered crystal structure forming by using FePO4 center dot 2H(2)O nanocrystallites as one of the raw materials. (C) 2012 Elsevier B.V. All rights reserved.
引用
收藏
页码:344 / 350
页数:7
相关论文
共 29 条
[1]   Electronically conductive phospho-olivines as lithium storage electrodes [J].
Chung, SY ;
Bloking, JT ;
Chiang, YM .
NATURE MATERIALS, 2002, 1 (02) :123-128
[2]   Electrochemical and electrical properties of Nb- and/or C-containing LiFePO4 composites [J].
Delacourt, C ;
Wurm, C ;
Laffont, L ;
Leriche, JB ;
Masquelier, C .
SOLID STATE IONICS, 2006, 177 (3-4) :333-341
[3]   One-step low-temperature route for the preparation of electrochemically active LiMnPO4 powders [J].
Delacourt, C ;
Poizot, P ;
Morcrette, M ;
Tarascon, JM ;
Masquelier, C .
CHEMISTRY OF MATERIALS, 2004, 16 (01) :93-99
[4]   KINETIC-ANALYSIS OF THERMAL-DECOMPOSITION REACTIONS .6. THERMAL-DECOMPOSITION OF MANGANESE(II) ACETATE TETRAHYDRATE [J].
DIEFALLAH, EM .
THERMOCHIMICA ACTA, 1992, 202 :1-16
[5]   Lithium battery materials LiMPO4 (M = Mn, Fe, Co, and Ni):: Insights into defect association, transport mechanisms, and doping behavior [J].
Fisher, Craig A. J. ;
Prieto, Veluz M. Hart ;
Islam, M. Saiful .
CHEMISTRY OF MATERIALS, 2008, 20 (18) :5907-5915
[6]   An optimized Ni doped LiFePO4/C nanocomposite with excellent rate performance [J].
Ge, Yucui ;
Yan, Xuedong ;
Liu, Jing ;
Zhang, Xianfa ;
Wang, Jiawei ;
He, Xingguang ;
Wang, Rongshun ;
Xie, Haiming .
ELECTROCHIMICA ACTA, 2010, 55 (20) :5886-5890
[7]   LiFexMn1-xPO4: A cathode for lithium-ion batteries [J].
Hong, Jian ;
Wang, Feng ;
Wang, Xiaoliang ;
Graetz, Jason .
JOURNAL OF POWER SOURCES, 2011, 196 (07) :3659-3663
[8]   Improving the electrochemical activity of LiMnPO4 via Mn-site co-substitution with Fe and Mg [J].
Hu, Chenglin ;
Yi, Huihua ;
Fang, Haisheng ;
Yang, Bin ;
Yao, Yaochun ;
Ma, Wenhui ;
Dai, Yongnian .
ELECTROCHEMISTRY COMMUNICATIONS, 2010, 12 (12) :1784-1787
[9]   Electrochemical Performance of LiMnPO4 Synthesized with Off-Stoichiometry [J].
Kang, Byoungwoo ;
Ceder, Gerbrand .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2010, 157 (07) :A808-A811
[10]   Electrochemical behavior of LiFePO4/C cathode material for rechargeable lithium batteries [J].
Liao, XZ ;
Ma, ZF ;
He, YS ;
Zhang, XM ;
Wang, L ;
Jiang, Y .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2005, 152 (10) :A1969-A1973