A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

• Published in: Journal of power sources 2018-01, Vol.373 (C), p.150-160
• Main Authors: Intan, Nadia N., Klyukin, Konstantin, Zimudzi, Tawanda J., Hickner, Michael A., Alexandrov, Vitaly
• Format: Article
• Language: English
• Subjects: ab–initio calculations; Infrared spectroscopy; Nafion; Vanadium redox flow batteries
• ISSN: 0378-7753; 1873-2755
• DOI: 10.1016/j.jpowsour.2017.10.050

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3− spectral region which is attributed to the interaction between vanadium species and the SO3− exchange sites. DFT calculations of vanadium−Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3− via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3−, which is not the case for VO2+ and VO2+. The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes. [Display omitted] •Nafion tends to have contact pair mechanism interactions with aqueous vanadium cations.•Strong cation binding to Nafion induces peak splitting observed in IR spectra.•DFT calculations help explain changes in IR spectra.