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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 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 and species coordinate spontaneously to SO 3 -, which is not the case for VO 2+ and VO 2 +. 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 inmore » light of previous results on device-cycled membranes.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [2];  [3]
  1. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemical and Biomolecular Engineering
  2. Pennsylvania State Univ., University Park, PA (United States). Dept. of Materials Science and Engineering
  3. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemical and Biomolecular Engineering and Nebraska Center for Materials and Nanoscience
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)”
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1545558
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
Subject:
Nafion; Vanadium redox flow batteries; ab–initio calculations; Infrared spectroscopyMSC:; 00-01; 99-00

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_1545558,
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 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 and 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.},
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}
}