skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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 spectral region which is attributed to the interaction between vanadium species and the 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 via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that and species coordinate spontaneously to , which is not the case for and . 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.

Authors:
; ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1478385
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 373; Journal Issue: C; Journal ID: ISSN 0378-7753
Country of Publication:
United States
Language:
English

Citation Formats

Intan, Nadia N., Klyukin, Konstantin, Zimudzi, Tawanda J., Hickner, Michael A., and Alexandrov, Vitaly. A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries. United States: N. p., 2018. Web. doi:10.1016/j.jpowsour.2017.10.050.
Intan, Nadia N., Klyukin, Konstantin, Zimudzi, Tawanda J., Hickner, Michael A., & Alexandrov, Vitaly. A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries. United States. doi:10.1016/j.jpowsour.2017.10.050.
Intan, Nadia N., Klyukin, Konstantin, Zimudzi, Tawanda J., Hickner, Michael A., and Alexandrov, Vitaly. Mon . "A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries". United States. doi:10.1016/j.jpowsour.2017.10.050.
@article{osti_1478385,
title = {A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries},
author = {Intan, Nadia N. and Klyukin, Konstantin and Zimudzi, Tawanda J. and Hickner, Michael A. and Alexandrov, Vitaly},
abstractNote = {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 spectral region which is attributed to the interaction between vanadium species and the 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 via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that and species coordinate spontaneously to , which is not the case for and . 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.},
doi = {10.1016/j.jpowsour.2017.10.050},
journal = {Journal of Power Sources},
issn = {0378-7753},
number = C,
volume = 373,
place = {United States},
year = {2018},
month = {1}
}