Multi-faceted highly crystalline LiMn2O4 and LiNi0.5Mn1.5O4 cathodes synthesized by a novel carbon exo-templating method

LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ powders have been synthesized by a novel cost-effective carbon exo-templating process. It has been observed that controlled nucleation in the pores of highly surface active carbon produces a distinct effect on the powder morphology and crystallinity. Quantitative X-ray phase analyses show single phase spinel structure having Fd3m symmetry for both samples. Field emission electron microscopy reveals particles of size 0.5–1.0 µm with well defined multi-faceted crystals. Cyclic voltammetry results show well separated distinct redox peaks at 4.05/3.92 and 4.17/4.08 V for LiMn₂O₄/Li and 4.91/4.61 V for LiNi_0.5Mn_1.5O₄/Li coin cells indicating good crystallinity and reversibility of the cathodes compared to that of pristine LiMn₂O₄ synthesized by conventional combustion process. The LiMn₂O₄/Li and LiNi_0.5Mn_1.5O₄/Li cells deliver an initial discharge capacity of 110 mA h/g and 122 mA h/g respectively at a current density of 0.05 mA/cm² and when cycled at 0.2 mA/cm², the cells maintain 81% and 96% of their initial discharge capacity respectively even after 20 cycles. On the other hand, at the same current density, LiMn₂O₄ synthesized by conventional combustion process suffers from severe capacity fading (only 37.5% capacity retention after the 25th cycle). The capacity fading rate is found to be very less even at further higher current densities (0.4–0.8 mA/cm²) for both LiMn₂O₄/Li and LiNi_0.5Mn_1.5O₄/Li cells synthesized by the templating process. The present study reveals that high crystallinity along with multi-faceted morphology shows a remarkable enhancement in capacity as well as rate performance of pristine LiMn₂O₄ and its Ni derivative.