From synthetic montroseite VOOH to topochemical paramontroseite VO2 and their applications in aqueous lithium ion batteries

Abstract

Synthetic montroseite VOOH has been successfully prepared via a simple template-free hydrothermal route on a large scale for the first time—after sixty years of delay. The as-obtained sample shows a hierarchical morphology of urchin-like nanoarchitecture with hollow interiors consisting of well-crystalline nanorods standing vertically on the shell surface. Time-dependent experiments illustrated that these hierarchical hollow nanourchins were formed through the hydrolysis-driven Kirkendall effect coupled with a new-phased vanadium oxyhydroxide V₁₀O₁₄(OH)₂ precursor templated approach. Meanwhile, the as-obtained VOOH hollow nanourchins could convert topochemically to paramontroseite VO₂ without altering the size and original appearance during the annealing process due to the extreme structural similarity revealed by crystal structure analysis. Furthermore, the improved electrochemical performance of both montroseite VOOH and paramontroseite VO₂ hierarchical hollow structures toward Li uptake and release verifies their potential applications as anode materials in aqueous lithium ion batteries. These improved electrochemical properties could be ascribed to the synergetic effect of the microscopic tunneled crystal structure and macroscopic hollow morphological features, which provide the easy infiltration of electrolyte, short diffusion lengths for lithium ions and electron transport as well as sufficient void space to buffer the volume change.