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
  • [1] Materials' effects on the elevated and room temperature performance of C/LiMn2O4 Li-ion batteries
    Amatucci, GG
    Schmutz, CN
    Blyr, A
    Sigala, C
    Gozdz, AS
    Larcher, D
    Tarascon, JM
    [J]. JOURNAL OF POWER SOURCES, 1997, 69 (1-2) : 11 - 25
  • [2] Preparation and electrochemical investigation of LiMn2-xMexO4 (Me:Ni, Fe, and x=0.5, 1) cathode materials for secondary lithium batteries
    Amine, K
    Tukamoto, H
    Yasuda, H
    Fujita, Y
    [J]. JOURNAL OF POWER SOURCES, 1997, 68 (02) : 604 - 608
  • [3] A new three-volt spinel Li1+xMn1.5Ni0.5O4 for secondary lithium batteries
    Amine, K
    Tukamoto, H
    Yasuda, H
    Fujita, Y
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (05) : 1607 - 1613
  • [4] Electrochemical investigations of cobalt-doped LiMn2O4 as cathode material for lithium-ion batteries
    Arora, P
    Popov, BN
    White, RE
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (03) : 807 - 815
  • [5] Common electroanalytical behavior of Li intercalation processes into graphite and transition metal oxides
    Aurbach, D
    Levi, MD
    Levi, E
    Teller, H
    Markovsky, B
    Salitra, G
    Heider, U
    Heider, L
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (09) : 3024 - 3034
  • [6] LiMn2-xCuxO4 spinels (0.1≤x≤0.5):: A new class of 5 V cathode materials for Li batteries -: I.: Electrochemical, structural, and spectroscopic studies
    Ein-Eli, Y
    Howard, WF
    Lu, SH
    Mukerjee, S
    McBreen, J
    Vaughey, JT
    Thackeray, MM
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (04) : 1238 - 1244
  • [7] LiNixCu0.5-xMn1.5O4 spinel electrodes, superior high-potential cathode materials for Li batteries -: I.: Electrochemical and structural studies
    Ein-Eli, Y
    Vaughey, JT
    Thackeray, MM
    Mukerjee, S
    Yang, XQ
    McBreen, J
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (03) : 908 - 913
  • [8] LiCuxIICuyIIIMn[2-(x+y])III,IVO4: 5V cathode materials
    EinEli, Y
    Howard, WF
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1997, 144 (08) : L205 - L207
  • [9] FEY GTK, IN PRESS MAT CHEM PH
  • [10] Correlation between the growth of the 3.3 V discharge plateau and capacity fading in Li1+xMn2-xO4 materials
    Gao, Y
    Dahn, JR
    [J]. SOLID STATE IONICS, 1996, 84 (1-2) : 33 - 40