Synthesis of Multicomponent Olivine by a Novel Mixed Transition Metal Oxalate Coprecipitation Method and Electrochemical Characterization

被引:59
作者
Park, Young-Uk
Kim, Jongsoon
Gwon, Hyeokjo
Seo, Dong-Hwa
Kim, Sung-Wook
Kang, Kisuk [1 ]
机构
[1] Korea Adv Inst Sci & Technol, Dept Mat Sci & Engn, Taejon 305701, South Korea
关键词
LITHIUM-ION BATTERIES; CATHODE MATERIALS; THERMAL-DECOMPOSITION; RECHARGEABLE BATTERIES; CRYSTAL-STRUCTURE; FERROUS OXALATE; INSERTION MATERIAL; PHASE-STABILITY; DIHYDRATE; KINETICS;
D O I
10.1021/cm903616d
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 multicomponent olivine cathode material. LiMn(1/3)Fe(1/3)Co(1/3)PO(4), was prepared via a novel coprecipitation method of the mixed transition metal oxalate, Mn(1/3)Fe(1/3)Co(1/3)(C(2)O(4))center dot 2H(2)O. The stoichiometric ratio and distribution of transition metals in the oxalate, therefore, in the olivine product, was affected sensitively by the environments in the coprecipitation process, while they are the important factors in determining the electrochemical property of electrode materials with multiple transition metals. The effect of the pH, atmosphere, temperature, and aging time was investigated thoroughly with respect to the atomic ratio of transition metals, phase purity, and morphology of the mixed transition metal oxalate. The electrochemical activity of each transition metal in the olivine synthesized through this method clearly was enhanced as indicated in the cyclic voltammetry (CV) and galvanostatic charge/discharge measurement Three distinctive contributions from Mn. Fe, and Co redox couples were detected reversibly in multiple charge and discharge processes. The first discharge capacity at the C/5 rate was 140 5 mAh g(-1) with good cycle retention The rate capability test showed that the high capacity still is retained even at the 4C and 6C rates with 102 and 81 mAh g(-1), respectively.
引用
收藏
页码:2573 / 2581
页数:9
相关论文
共 48 条
[21]   Mixed layered Ni-Mn-Co hydroxides: Crystal structure, electronic state of ions, and thermal decomposition [J].
Kosova, N. V. ;
Devyatkina, E. T. ;
Kaichev, V. V. .
JOURNAL OF POWER SOURCES, 2007, 174 (02) :735-740
[22]   Effect of Co2P on electrochemical performance of Li(Mn0.35Co0.2Fe0.45)PO4/C [J].
Kuo, H. T. ;
Chan, T. S. ;
Bagkar, N. C. ;
Liu, G. Q. ;
Liu, R. S. ;
Shen, C. H. ;
Shy, A. S. ;
Xing, X. K. ;
Chen, J. M. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2008, 112 (27) :8017-8023
[23]   Effect of synthesis method on the electrochemical performance of LiNi1/3Mn1/3Co1/3O2 [J].
Li, DC ;
Muta, T ;
Zhang, LQ ;
Yoshio, M ;
Noguchi, H .
JOURNAL OF POWER SOURCES, 2004, 132 (1-2) :150-155
[24]   LiMnPO4 as the cathode for lithium batteries [J].
Li, GH ;
Azuma, H ;
Tohda, M .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2002, 5 (06) :A135-A137
[25]   Novel synthesis route for LiFePO4/C cathode materials for lithium-ion batteries [J].
Liao, XZ ;
Ma, ZF ;
Wang, L ;
Zhang, XM ;
Jiang, Y ;
He, YS .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2004, 7 (12) :A522-A525
[26]   Synthesis and characterization of LiNi1-x-yCoxMnyO2 as the cathode materials of secondary lithium batteries [J].
Liu, ZL ;
Yu, AS ;
Lee, JY .
JOURNAL OF POWER SOURCES, 1999, 81 :416-419
[27]   Layered cathode materials Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2 for lithium-ion batteries [J].
Lu, ZH ;
MacNeil, DD ;
Dahn, JR .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2001, 4 (11) :A191-A194
[28]   A study on isothermal kinetics of thermal decomposition of cobalt oxalate to cobalt [J].
Majumdar, S. ;
Sharma, I. G. ;
Bidaye, A. C. ;
Suri, A. K. .
THERMOCHIMICA ACTA, 2008, 473 (1-2) :45-49
[29]   In situ X-ray absorption and diffraction studies of carbon coated LiFe1/4Mn1/4Co1/4Ni1/4PO4 cathode during first charge [J].
Nam, Kyung-Wan ;
Wang, Xiao-Jian ;
Yoon, Won-Sub ;
Li, Hong ;
Huang, Xuejie ;
Haas, Otto ;
Bai, Jianming ;
Yang, Xiao-Qing .
ELECTROCHEMISTRY COMMUNICATIONS, 2009, 11 (04) :913-916
[30]   THERMAL DECOMPOSITION OF FERROUS OXALATE DIHYDRATE [J].
NICHOLSON, GC .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1967, 29 (07) :1599-+