Structure, hydrolysis and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

TL;DR

This study uses advanced molecular dynamics simulations to analyze the hydration, hydrolysis, and diffusion of vanadium ions in water, providing insights relevant for improving vanadium redox flow batteries.

Contribution

It offers detailed molecular-level insights into vanadium ion behavior in aqueous solutions, including hydration structures, hydrolysis constants, and diffusion, based on first-principles simulations.

Findings

V$^{2+}$ and V$^{3+}$ have six water molecules in their hydration shells.

Hydrolysis constants vary among vanadium ions, affecting their chemical behavior.

Chloride ions influence hydrolysis and reduce oxide precipitation risk.

Abstract

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries (RFB). Here, we employ Car-Parrinello molecular dynamics (CPMD) simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction and diffusion of aqueous V$^{2+}$, V$^{3+}$, VO$^{2+}$, and VO$_2^+$ ions at 300 K. The results indicate that the first hydration shell of both V$^{2+}$ and V$^{3+}$ contains six water molecules, while VO$^{2+}$ is coordinated to five and VO$_2^+$ to three water ligands. The first acidity constants (p$K_\mathrm{a}$) estimated using metadynamics simulations are 2.47, 3.06 and 5.38 for aqueous V$^{3+}$, VO$_2^+$ and VO$^{2+}$, respectively, while V$^{2+}$ is predicted to be a fairly weak acid in aqueous solution with a p$K_\mathrm{a}$ value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO$_2^+$ ion has a significant impact on water hydrolysis leading to a much higher p$K_\mathrm{a}$ value of 4.8. This should result in a lower propensity of aqueous VO$_2^+$ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V$^{3+}$ $<$ VO$_2^+$ $<$ VO$^{2+}$ $<$ V$^{2+}$ and thus correlate with the simulated hydrolysis constants, namely, the higher the p$K_\mathrm{a}$ value, the greater the diffusion coefficient.