Carbothermal synthesis, spectral and magnetic characterization and Li-cyclability of the Mo-cluster compounds, LiYMo3O8 and Mn2Mo3O8

被引:80
作者
Das, B. [1 ]
Reddy, M. V. [1 ]
Krishnamoorthi, C. [1 ]
Tripathy, S. [2 ]
Mahendiran, R. [1 ]
Rao, G. V. Subba [1 ]
Chowdari, B. V. R. [1 ]
机构
[1] Natl Univ Singapore, Dept Phys, Singapore 117542, Singapore
[2] ASTAR, Inst Mat Res & Engn, Singapore 117602, Singapore
关键词
LiYMo3O8; Mn2Mo3O8; Carbothermal reduction; FT-IR spectra; Raman spectra; Magnetic properties; Li-cycling; ANODE MATERIALS; INSERTION PROPERTIES; NEUTRON-DIFFRACTION; NEGATIVE-ELECTRODE; LITHIUM; OXIDES; MOLYBDENUM; PERFORMANCE; REDUCTION; BATTERIES;
D O I
10.1016/j.electacta.2008.12.049
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The molybdenum cluster compounds, LiYMo3O8 and Mn2Mo3O8 are prepared by the carbothermal reduction method and characterized by various techniques. The FT-IR at ambient temperature (RT), and Raman spectra at various temperatures (78-450 K) are reported for the first time and results are interpreted. Magnetic studies on Mn2Mo3O8 in the temperature range, 10-350 K confirm that it is ferrimagnetic, with T-C = 39 K. Magnetic hysteresis and magnetization data at various fields and temperatures are presented. The Li-cyclability is investigated by galvanostatic cycling in the voltage range. 0.005-3.0V vs. Li at 30 mA/g (0.08 C). LiYMo3O8 shows a total first-discharge capacity of 305 +/- 5 mAh/g whereas the first-charge capacity is only 180 mAh/g at RT. However, both values increased systematically with an increase in the cycle number and yielded a reversible capacity of 385 5 mAh/g at the end of 120th cycle. At 50 degrees C, the reversible capacity is 418 +/- 5 mAh/g at the 60th cycle. The coulombic efficiency ranges from 94% to 98%. The Li-cyclability behavior of Mn2Mo3O8 is entirely different from that of LiYMo3O8. The total first-discharge and charge capacities are 710 +/- 5 and 565 +/- 5 mAh/g, but drastic capacity-fading occurs during cycling. The reversible capacity at the end of 50th cycle is only 205 +/- 5 mAh/g. Plausible reaction mechanisms are proposed and discussed based on the galavanostatic cycling, cyclic voltammetry, ex situ XRD, ex situ TEM and impedance spectral data. (C) 2009 Published by Elsevier Ltd.
引用
收藏
页码:3360 / 3373
页数:14
相关论文
共 42 条
[1]   Nanostructured materials for advanced energy conversion and storage devices [J].
Aricò, AS ;
Bruce, P ;
Scrosati, B ;
Tarascon, JM ;
Van Schalkwijk, W .
NATURE MATERIALS, 2005, 4 (05) :366-377
[2]   Nanoparticles of SnO produced by sonochemistry as anode materials for rechargeable lithium batteries [J].
Aurbach, D ;
Nimberger, A ;
Markovsky, B ;
Levi, E ;
Sominski, E ;
Gedanken, A .
CHEMISTRY OF MATERIALS, 2002, 14 (10) :4155-4163
[3]   Synthesis and electrochemical insertion properties of the layered LixMoO2 phases (x = 0.74, 0.85, and 1.00) [J].
Barker, J ;
Saidi, MY ;
Swoyer, JL .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2003, 6 (12) :A252-A256
[4]   Lithium insertion properties of the layered LiMoO2R(3)over-bar-m made by a novel carbothermal reduction method [J].
Barker, J ;
Saidi, MY ;
Swoyer, JL .
SOLID STATE IONICS, 2003, 158 (3-4) :261-267
[5]   STRUCTURAL AND MAGNETIC STUDY OF IRON-GROUP MOLYBDATES [J].
BERTRAND, D ;
KERNERCZESKLEBA, H .
JOURNAL DE PHYSIQUE, 1975, 36 (05) :379-390
[6]   Nanomaterials for rechargeable lithium batteries [J].
Bruce, Peter G. ;
Scrosati, Bruno ;
Tarascon, Jean-Marie .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (16) :2930-2946
[7]   Novel tin oxide spinel-based anodes for Li-ion batteries [J].
Conner, PA ;
Irvine, JTS .
JOURNAL OF POWER SOURCES, 2001, 97-8 :223-225
[8]   Synthesis of Mo-cluster compound, LiHoMo3O8 by carbothermal reduction and its reactivity towards Li [J].
Das, B. ;
Reddy, M. V. ;
Rao, G. V. Subba ;
Chowdari, B. V. R. .
JOURNAL OF SOLID STATE ELECTROCHEMISTRY, 2008, 12 (7-8) :953-959
[9]   COMPLEX METAL OXIDES OF TYPE AMMO43O8 [J].
DEBENEDITTIS, J ;
KATZ, L .
INORGANIC CHEMISTRY, 1965, 4 (12) :1836-+
[10]   Magnetism in carbon structures [J].
Esquinazi, P ;
Höhn, R .
JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS, 2005, 290 :20-27