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

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

doi:10.1016/j.jpowsour.2017.10.050

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

Journal Article · Thu Nov 09 00:00:00 EST 2017 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2017.10.050· OSTI ID:1478385

Intan, Nadia N. ^[1]; ^[1]; ^[2]; Hickner, Michael A. ^[2]; Alexandrov, Vitaly ^[1]

Univ. of Nebraska, Lincoln, NE (United States)
Pennsylvania State Univ., University Park, PA (United States)

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 SO$$^-_3$$ spectral region which is attributed to the interaction between vanadium species and the SO$$^-_3$$ 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 SO$$^-_3$$ 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 SO$$^-_3$$, which is not the case for VO²⁺ and VO$$^+_2$$. In conclusion, 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Wind Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1478385

Alternate ID(s):: OSTI ID: 1545558
OSTI ID: 1548852

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Journal Issue: C Vol. 373; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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