Fey, G.T.K. and Lu, C.Z. and Premkumar, T. (2003) Solid-state synthesis and electrochemical characterization of LiMyCr0.5−yMn1.5O4 (M = Fe or Al; 0.0 < y < 0.4) spinels. Materials Chemistry and Physics, 80. pp. 309-318. ISSN 0254-0584

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A series of LiMyCr0.5−yMn1.5O4 compositions, whereMis either Fe or Al, was synthesized by a conventional solid-state fusion method. Phase-pure materials were obtained for all the Fe-substituted compositions, while at Al stoichiometries of 0.3 and 0.4 the Al-substituted compositions had –LiAlO2 as an impurity phase. An increase in the amount of Fe or Al increased the lattice parameters as well as the propensity of these co-dopants to occupy the 8a lithium sites. Electrochemical activity was noted in the 4 and 5-V regions. Fe as a co-substituent increased the currents associated with the high-voltage peaks, while Al as a co-substituent enhanced the high-voltage capability of the spinel. Irrespective of whether the co-substituentwas a transition metal or non-transition metal, it altered the electrochemical characteristics of both the Mn4+/Mn3+ and the Cr4+/Cr3+ couples, the effect being more pronounced in the 5-V region. Although increased amounts of Fe or Al rendered the spinels high-voltage active, both the deliverable capacity and capacity retention were lowered. The cumulative capacity obtained with Al-substituted materials was less than with Fe-substituted materials. At a 0.1 C rate between 3.3 and 5.1V, the Fe co-substituted spinel (y = 0.1) gave a first-cycle capacity of 117 mAh g−1, while that with Al was 112 mAh g−1. The corresponding values in the 40th cycle were 88 and 82 mAh g−1.

Item Type: Article
Uncontrolled Keywords: LiMn2O4; Substituted LiMn2O4; Oxide cathodes; Lithium intercalation; Lithium-ion battery
Subjects: Lithium batteries
Depositing User: ttbdar CECRI
Date Deposited: 05 Apr 2012 11:21
Last Modified: 05 Apr 2012 11:21
URI: http://cecri.csircentral.net/id/eprint/894

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