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Title: First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery

Abstract

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (11[2 with combining macron]0) graphite facets with water and aqueous V2+/V3+ redox species at 300 K employing Car–Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V2+/V3+ species. The formation of V–O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]
  1. Department of Chemical and Biomolecular Engineering; University of Nebraska-Lincoln; Lincoln; USA
  2. Department of Chemical and Biomolecular Engineering; University of Nebraska-Lincoln; Lincoln; USA; Nebraska Center for Materials and Nanoscience
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492389
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 19; Journal Issue: 23; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
English

Citation Formats

Jiang, Zhen, Klyukin, Konstantin, and Alexandrov, Vitaly. First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery. United States: N. p., 2017. Web. doi:10.1039/c7cp02350b.
Jiang, Zhen, Klyukin, Konstantin, & Alexandrov, Vitaly. First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery. United States. doi:10.1039/c7cp02350b.
Jiang, Zhen, Klyukin, Konstantin, and Alexandrov, Vitaly. Sun . "First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery". United States. doi:10.1039/c7cp02350b.
@article{osti_1492389,
title = {First-principles study of adsorption–desorption kinetics of aqueous V 2+ /V 3+ redox species on graphite in a vanadium redox flow battery},
author = {Jiang, Zhen and Klyukin, Konstantin and Alexandrov, Vitaly},
abstractNote = {Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (11[2 with combining macron]0) graphite facets with water and aqueous V2+/V3+ redox species at 300 K employing Car–Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V2+/V3+ species. The formation of V–O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.},
doi = {10.1039/c7cp02350b},
journal = {Physical Chemistry Chemical Physics},
issn = {1463-9076},
number = 23,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

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