Preparation and electrochemical properties of high-voltage cathode materials, LiMyNi0.5-yMn1.5O4 (M = Fe, Cu, Al, Mg; y=0.0-0.4)

被引:168
作者
Fey, GTK [1 ]
Lu, CZ [1 ]
Kumar, TP [1 ]
机构
[1] Natl Cent Univ, Dept Chem & Mat Engn, Chungli 32054, Taiwan
关键词
multiple substitution; cathode materials; LiMn2O4; spinel cathode; lithium battery;
D O I
10.1016/S0378-7753(03)00010-7
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
Solid-state synthesized LiNi0.5-yMyMn1.5O4 spinels, where M - Fe, Mg, Al, or Cu, and y = 0.0-0.4, have been studied as high-voltage cathode materials. Powder X-ray diffraction studies showed that all the substituents displayed a propensity for the 8a tetrahedral site at high concentrations. Cyclic voltammetric studies showed electrochemical activity around 4 V as well as above 4.4 V. While the 4-V activity was related solely to the Mn4+/Mn3+ couple, the 5-V activity was due to the redox reactions of Ni and the other transition metal ions. The cosubstituents reduced the 5-V capacity and shifted the redox potentials in the 5-V region to higher values. At high concentrations, the cosubstituents tended to occupy the 8a sites, which may lead to a blockage of lithium transport during the charge-discharge processes. LiNi0.4Fe0.1Mn1.5O4 registered the best performance with a first-cycle capacity of 117 mAh/g and 78% capacity retention over 60 cycles. Electrochemical impedance spectroscopic studies showed a decrease in the charge transfer resistance at high deintercalation levels. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:332 / 345
页数:14
相关论文
共 41 条
  • [11] Changes in the voltage profile of Li/Li1+xMn2-xO4 cells as a function of x
    Gao, Y
    Reimers, JN
    Dahn, JR
    [J]. PHYSICAL REVIEW B, 1996, 54 (06): : 3878 - 3883
  • [12] IMPROVED CAPACITY RETENTION IN RECHARGEABLE 4V LITHIUM LITHIUM MANGANESE OXIDE (SPINEL) CELLS
    GUMMOW, RJ
    DEKOCK, A
    THACKERAY, MM
    [J]. SOLID STATE IONICS, 1994, 69 (01) : 59 - 67
  • [13] Cathode of LiMgyMn2-yO4 and LiMgyMn2-yO4-δ spinel phases for lithium secondary batteries
    Hayashi, N
    Ikuta, H
    Wakihara, M
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (04) : 1351 - 1354
  • [14] Dissolution of spinel oxides and capacity losses in 4V Li/LixMn2O4 coils
    Jang, DH
    Shin, YJ
    Oh, SM
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (07) : 2204 - 2211
  • [15] LiAlyCo1-yO2 (R(3)over-bar-m) intercalation cathode for rechargeable lithium batteries
    Jang, YI
    Huang, BY
    Wang, HF
    Sadoway, DR
    Ceder, G
    Chiang, YM
    Liu, H
    Tamura, H
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (03) : 862 - 868
  • [16] THE PREPARATION, CRYSTALLOGRAPHY, AND MAGNETIC PROPERTIES OF THE LIXCO(1-X)O SYSTEM
    JOHNSTON, WD
    HEIKES, RR
    SESTRICH, D
    [J]. JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 1958, 7 (01) : 1 - 13
  • [17] High-voltage lithium cathode materials
    Kawai, H
    Nagata, M
    Tukamoto, H
    West, AR
    [J]. JOURNAL OF POWER SOURCES, 1999, 81 : 67 - 72
  • [18] LECRAS F, 1996, SOLID STATE IONICS, V203, P89
  • [19] Degradation mechanisms in doped spinels of LiM0.05Mn1.95O4 (M = Li, B, Al, Co, and Ni) for Li secondary batteries
    Lee, JH
    Hong, JK
    Jang, DH
    Sun, YK
    Oh, SM
    [J]. JOURNAL OF POWER SOURCES, 2000, 89 (01) : 7 - 14
  • [20] Unique aluminum effect of LiAlxMn2-xO4 material in the 3 V region
    Lee, YS
    Yoshio, M
    [J]. ELECTROCHEMICAL AND SOLID STATE LETTERS, 2001, 4 (07) : A85 - A88