Strategies to alleviate distortive phase transformations in Li-ion intercalation reactions: an example with vanadium pentoxide

Abstract

Chemical and electrochemical Li-ion insertion in transition metal oxides, either via a phase transformation reaction (ions insert into specific crystallographic sites of the host lattice) or a solid solution insertion (ions distribute uniformly throughout the host lattice), enables high energy density electrochemical energy storage. Many phase transformation cathode materials, that undergo two-phase reactions, exhibit high theoretical capacities arising from multi-electron redox reactions. However, challenges in distortive phase transformations and uncontrolled phase nucleation, propagation, segregation, and co-existence continue to limit the energy density, (dis)charging rate performances, and cycling stability of available phase transformation cathode materials. Vanadium pentoxide (V₂O₅), a classical layered intercalation host material with high theoretical capacity, undergoes irreversible structural changes and capacity fading when intercalating more than one lithium ion per V₂O₅ unit in its thermodynamically stable phase. Here, we review recent synthetic strategies to alter the V–O connectivity, thereby alleviating distortive phase transformations and promoting solid solution-based Li-ion insertion in V₂O₅. We also summarize several widely accessible and classical molecular-based analytical tools that can provide local structural dynamics and phase transformation mechanism information on the lithiation of V₂O₅, including single-crystal X-ray diffraction, infrared and Raman spectroscopy, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopy.