Probing the Physicochemical Behavior of Variously Doped Li₄Ti₅O₁₂ Nanoflowers

This study thoroughly investigated the synthesis of not only 4 triply-doped metal oxides but also 5 singly-doped analogues of Li₄Ti₅O₁₂ for electrochemical applications. In terms of synthetic novelty, the triply-doped materials were fabricated using a relatively facile hydrothermal method for the first-time, involving the simultaneous substitution of Ca for the Li site, Ln (i.e., Dy, Y, or Gd) for the Ti site, and Cl for the O site. Based on XRD, SEM, and HRTEM-EDS measurements, the resulting materials, incorporating a relatively homogeneous and uniform dispersion of both the single and triple dopants, exhibited a micron-scale flower-like morphology that remained apparently undamaged by the doping process. Crucially, the surface chemistry of all of the samples was probed using XPS in order to analyze any nuanced changes associated with either the various different lanthanide dopants or the identity of the metal precursor types involved. In the latter case, it was observed that the use of a nitrate salt precursor versus that of a chloride salt enabled not only a higher lanthanide incorporation but also the potential for favorable N-doping, all of which promoted a concomitant increase in conductivity due to a perceptible increase in Ti³⁺ content. In terms of the choice of lanthanide system, it was observed via CV analysis that dopant incorporation generally (albeit with some notable exceptions, especially with Y-based materials) led to the formation of higher amounts of Ti³⁺ species within both the singly and triply-doped materials, which consequentially led to the potential for increased diffusivity and higher mobility of Li⁺ species with the possibility for enabling greater capacity within these classes of metal oxides.