New ramsdellites LiTi 2−yV yO 4 (0≤ y≤1): Synthesis, structure, magnetic properties and electrochemical performances as electrode materials for lithium batteries

Abstract

The new ramsdellite series LiTi 2− y V y O 4 (0≤ y≤1) has been prepared by conventional solid state chemistry techniques and was characterized by X-ray powder diffraction and electron diffraction. To our knowledge, this is the first report on ramsdellites containing vanadium. The magnetic behaviour of these ramsdellites is strongly influenced by its vanadium content. In this sense, LiTi 2O 4 ( y=0) exhibits metallic-like temperature independent paramagnetism, but d electrons tend to localize with increasing V content. LiTiVO 4, though also paramagnetic, follows then the Curie–Weiss law. The crossover from delocalized to localized electrons is observed between compositions y=0.6 and 0.8. For y≥0.8 the magnetic results evidence an isovalent substitution mechanism of trivalent Ti by V. The electrochemical lithium intercalation and deintercalation chemistry of LiTi 2− y V y O 4 is grouped into two different operating voltage regions. Reversible lithium deintercalation of vanadium-substituted ramsdellite titanates LiTi 2− y V y O 4 in the high voltage range 2–3 V vs. Li occurs in two main steps, one at about 2 V and the other at about 3 V. The 3 V process capacity increases with the vanadium content, while the 2 V capacity decreases at the same time. The vanadium to titanium substitution rate in LiTi 2O 4 was found to be beneficial to the specific energy in as much as a 50% increase (1 V) of the working voltage is observed. On the other hand, reversible lithium intercalation in vanadium-substituted ramsdellite titanates LiTi 2− y V y O 4 in the low voltage range 1–2 V vs. Li occurs in one main single step, in which the capacity is not affected by the vanadium content, although vanadium-doping produces an improved capacity retention with an excellent cycling behaviour observed for y≤0.6.