Abstract
A study on the structural and electrochemical properties of LiCr0.2Mn1.8O4 and LiV0.2Cr0.2Mn1.6O4 cathodes has been made with a view to understand the effect of mono- (Cr) and bication (Cr and V) substitution on LiMn2O4 spinel individually. Citric acid assisted modified sol–gel method has been followed to synthesize a series of LiMn2O4, LiCr0.2Mn1.8O4, and LiV0.2Cr0.2Mn1.6O4 cathodes, and the corresponding lattice structure, surface morphology, and site occupancy of lithium in the spinel matrix are acknowledged using X-ray diffraction, scanning electron microscopy, and magic angle spinning 7Li nuclear magnetic resonance results. The site occupancy of Cr3+ in the 16d octahedral and that of V5+ in the 16d octahedral and 8a tetrahedral positions are understood. Electrochemical cycling studies of LiCr0.2Mn1.8O4 cathode demonstrate an enhanced structural stability and better capacity retention (94%) resulting from the Cr3+ dopant-induced co-valency of Li-O-Mn bond. On the other hand, simultaneous substitution of Cr and V in LiV0.2Cr0.2Mn1.6O4 has failed to improve the electrochemical properties of native LiMn2O4 spinel cathode, mainly due to vanadium-driven cation mixing and the reduced lithium diffusion kinetics. Among the candidates chosen for the study, LiCr0.2Mn1.8O4 qualifies itself as a better cathode for rechargeable lithium battery applications.
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The authors are thankful to the Department of Science and Technology (DST), India for the financial support to carry out this work.
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Jayaprakash, N., Kalaiselvi, N., Gangulibabu et al. Effect of mono- (Cr) and bication (Cr, V) substitution on LiMn2O4 spinel cathodes. J Solid State Electrochem 15, 1243–1251 (2011). https://doi.org/10.1007/s10008-010-1194-6
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DOI: https://doi.org/10.1007/s10008-010-1194-6