In this study, the '-V 2 O 5 cathode material was prepared through a solution synthesis technique leading to homogeneous, fine and porous particles 100-200 nm in size. This successful preparation allows to overcome the huge drawback of the microsized material in terms of charge efficiency and to take benefit of the attractive Na insertion properties of '-V 2 O 5, i. e. a significant available capacity of 145 mAh g -1 , a high working potential of about 3.25 V vs. Na + /Na, an excellent charge efficiency, a high-rate capability and good cycle life.

A detailed structural study upon Na insertion/extraction shows that the proposed nanosizing approach promotes a homogeneous Na solubility and solid solution behavior in a wider composition range (0.4 < x ≤ 1 in -Na x V 2 O 5 ) compared to the results previously reported for solid-state synthesized '-V 2 O 5 . Furthermore, highly reversible structural changes are evidenced. Key kinetic parameters governing the Na insertion-extraction reaction are discussed thanks to an impedance spectroscopy study revealing a faster Na diffusivity in the one-phase region. The obtained results allow a comprehensive understanding of the enhanced performance exhibited by the present sub-micronic '-V 2 O 5 material.