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

Nadia N. Intan, Konstantin Klyukin, Tawanda Zimudzi, Michael Anthony Hickner, Vitaly Alexandrov

Research output: Contribution to journalArticle

7 Citations (Scopus)

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 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.

Original languageEnglish (US)
Pages (from-to)150-160
Number of pages11
JournalJournal of Power Sources
Volume373
DOIs
StatePublished - Jan 1 2018

Fingerprint

Vanadium
vanadium
electric batteries
Ions
membranes
Membranes
ions
interactions
Cations
Positive ions
cations
Density functional theory
Molecular dynamics
molecular dynamics
density functional theory
Flow batteries
perfluorosulfonic acid
Vibrational spectra
energy storage
Energy storage

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering

Cite this

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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 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.",
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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; Hickner, Michael Anthony; Alexandrov, Vitaly.

In: Journal of Power Sources, Vol. 373, 01.01.2018, p. 150-160.

Research output: Contribution to journalArticle

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AU - Alexandrov, Vitaly

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