Anomalous capacity and cycling stability of xLi2MnO3•(1-x)LiMO2 electrodes (M = Mn, Ni, Co) in lithium batteries at 50°C

被引:385
作者
Johnson, Christopher S. [1 ]
Li, Naichao [1 ]
Lefief, Christina [1 ]
Thackeray, Michael M. [1 ]
机构
[1] Argonne Natl Lab, Electrochem Technol Program, Div Chem Engn, Argonne, IL 60439 USA
关键词
lithium battery; cathode; composite structure; Li2MnO3; LiMn0.5Ni0.5O2; LiMn0.33Ni0.33Co0.33O2;
D O I
10.1016/j.elecom.2006.11.006
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Transition metal oxides with composite xLi(2)MnO(3). (1 - x)LiMO2 rocksalt structures (M = Mn, Ni, Co) are of interest as a new generation of cathode materials for high energy density lithium-ion batteries. After electrochemical activation to 4.6 or 4.8 V (vs. Li-0) at 50 degrees C, xLi(2)MnO(3). (1 - x)LiMn0.33Ni0.33Co0.33O2 (x = 0.5, 0.7) electrodes deliver initial discharge capacities (> 300 mAh/g) at a low current rate (0.05 mA/cm(2)) that exceed the theoretical values for lithiation back to the rocksalt stoichiometry (240-260 mAh/g), at least during the early charge/discharge cycles of the cells. Attention is drawn to previous reports of similar, but unaccounted and unexplained anomalous behavior of these types of electrode materials. Possible reasons for this anomalous capacity are suggested. Indications are that electrodes in which M = Mn, Ni and Co do not cycle with the same stability at 50 degrees C as those without cobalt. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:787 / 795
页数:9
相关论文
共 35 条
  • [1] Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2
    Armstrong, A. Robert
    Holzapfel, Michael
    Novak, Petr
    Johnson, Christopher S.
    Kang, Sun-Ho
    Thackeray, Michael M.
    Bruce, Peter G.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (26) : 8694 - 8698
  • [2] Overcharging manganese oxides:: Extracting lithium beyond Mn4+
    Armstrong, AR
    Robertson, AD
    Bruce, PG
    [J]. JOURNAL OF POWER SOURCES, 2005, 146 (1-2) : 275 - 280
  • [3] Electrochemistry beyond Mn4+ in LixMn1-yLiyO2
    Armstrong, AR
    Bruce, PG
    [J]. ELECTROCHEMICAL AND SOLID STATE LETTERS, 2004, 7 (01) : A1 - A4
  • [4] Theory of overlithiation reaction in LiMO2 battery electrodes
    Benedek, R
    Vaughey, J
    Thackeray, MM
    [J]. CHEMISTRY OF MATERIALS, 2006, 18 (05) : 1296 - 1302
  • [5] High-resolution X-ray diffraction, DIFFaX, NMR and first principles study of disorder in the Li2MnO3-Li[Ni1/2Mn1/2]O2 solid solution
    Bréger, J
    Jiang, M
    Dupré, N
    Meng, YS
    Shao-Horn, Y
    Ceder, G
    Grey, CP
    [J]. JOURNAL OF SOLID STATE CHEMISTRY, 2005, 178 (09) : 2575 - 2585
  • [6] Short- and long-range order in the positive electrode material, Li(NiMn)0.5O2:: A joint X-ray and neutron diffraction, pair distribution function analysis and NMR study
    Bréger, J
    Dupré, N
    Chupas, PJ
    Lee, PL
    Proffen, T
    Parise, JB
    Grey, CP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (20) : 7529 - 7537
  • [7] Comparison of metal ion dissolutions from lithium ion battery cathodes
    Choi, W.
    Manthiram, A.
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2006, 153 (09) : A1760 - A1764
  • [8] Structure, electrochemical properties, and thermal stability studies of cathode materials in the xLi[Mn1/2Ni1/2]O2•yLiCoO2•zLi[Li1/3Mn2/3]O2 pseudoternary system, (x+y+z=1)
    Jiang, J
    Eberman, KW
    Krause, LJ
    Dahn, JR
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2005, 152 (09) : A1879 - A1889
  • [9] Insignificant impact of designed oxygen release from high capacity Li[(Ni1/2Mn1/2)xCoy(Li1/3Mn2/3)1/3]O2 (x+y=2/3) positive electrodes during the cycling of Li-ion cells
    Jiang, J
    Dahn, JR
    [J]. ELECTROCHIMICA ACTA, 2006, 51 (17) : 3413 - 3416
  • [10] JOHNSON CHJ, UNPUB