Enhanced Electrochemical Performance of Rare-Earth Metal-Ion-Doped Nanocrystalline LiTiO Electrodes in High-Power Li-Ion Batteries.

A comprehensive and comparative exploration research performed, aiming to elucidate the fundamental mechanisms of rare-earth (RE) metal-ion doping into LiTiO (LTO), reveals the enhanced electrochemical performance of the nanocrystalline RE-LTO electrodes in high-power Li-ion batteries. Pristi ne LiTiO (LTO) and rare-earth metal-doped LiTiLnO (RE-LTO with RE = Dy, Ce, Nd, Sm, and Eu; ≈ 0.1) nanocrystalline anode materials were synthesized using a simple mechanochemical method and subsequent calcination at 850 °C. The X-ray diffraction (XRD) patterns of pristine and RE-LTO samples exhibit predominant (111) orientation along with other characteristic peaks corresponding to cubic spinel lattice. No evidence of RE-doping-induced changes was seen in the crystal structure and phase. The average crystallite size for pristine and RE-LTO samples varies in the range of 50-40 nm, confirming the formation of nanoscale crystalline materials and revealing the good efficiency of the ball-milling-assisted process adopted to synthesize nanoscale particles. Raman spectroscopic analyses of the chemical bonding indicate and further validate the phase structural quality in addition to corroborating with XRD data for the cubic spinel structure formation. Transmission electron microscopy (TEM) reveals that both pristine and RE-LTO particles have a similar cubic shape, but RE-LTO particles are better interconnected, which provide a high specific surface area for enhanced Li-ion storage. The detailed electrochemical characterization confirms that the RE-LTO electrodes constitute promising anode materials for high-power Li-ion batteries. The RE-LTO electrodes deliver better discharge capacities (in the range of 172-198 mAh g at 1C rate) than virgin LTO (168 mAh g). Among them, Eu-LTO provides the best discharge capacity of 198 mAh g at a 1C rate. When cycled at a high current rate of 50C, all RE-LTO electrodes show nearly 70% of their initial discharge capacities, resulting in higher rate capability than virgin LTO (63%). The results discussed in this work unfold the fundamental mechanisms of RE doping into LTO and demonstrate the enhanced electrochemical performance derived chemical composition tailoring in RE-LTO compounds for application in high-power Li-ion batteries.