Comparative study of the phase transition of Li1+xMn2-xO4 by anelastic spectroscopy and differential scanning calorimetry

Li1+xMn2-xO4 is one of the most promising candidates as high performance cathode for lithium ion batteries. The stoichiometric compound is known to undergo a phase transition around room temperature, which has been widely studied and attributed either to Jahn-Teller effect or to charge ordering. For the applications it is important to suppress this phase transition, which lowers the electrochemical performances of the material. DSC measurements, which have been largely used in the literature to study the occurrence of the transformation, can detect a phase transition accompanied by latent heat only for x < 0.04. This fact has been generally accepted as a proof that the transformation is suppressed by doping. However, by using a technique extremely sensitive to rearrangements of atoms in the lattice, such as anelastic spectroscopy, we show that the phase transition persists up to x = 0.08, is shifted to lower temperatures, and changes its nature from first to higher order. The implications for the mechanism driving the transition and the similarities and differences with doped Fe3O4, which is the prototype of charge order transitions, are discussed.