Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes

Yamamura, Tomoo; Watanabe, N.; Yano, Takashi; Shiokawa, Yoshinobu

doi:10.1149/1.1870794

Cited by 210 publications

(122 citation statements)

References 45 publications

Supporting

Mentioning

107

Contrasting

Order By: Relevance

“…Ref. [30] Initial vanadium concentration Fig. 3 shows the simulated negative electrode potentials by two-dimensional model [16] and the ones by threedimensional model at different SOC for applied current density of 40 mA cm −2 .…”

Section: Numerical Details and Parametersmentioning

confidence: 99%

A three-dimensional model for negative half cell of the vanadium redox flow battery

Zhang

Xing

2011

Electrochimica Acta

171

View full text Add to dashboard Cite

Section: Numerical Details and Parametersmentioning

confidence: 99%

A three-dimensional model for negative half cell of the vanadium redox flow battery

Zhang

Xing

2011

Electrochimica Acta

171

View full text Add to dashboard Cite

“…20 One group concluded that the kinetics for the VO 2+ /VO 2 + reaction are faster than the V 2+ /V 3+ reaction at a plastic formed carbon electrode, but found the opposite when using pyrolytic graphite. 21 Previously, we reported that electrochemical oxidation treatments enhanced the V 2+ /V 3+ reaction kinetics, whereas electrochemical reduction treatments enhanced the VO 2+ /VO 2 + reaction kinetics. 22,23 This was demonstrated using a range of carbon materials including glassy carbon, carbon paper, carbon xerogel, and carbon fiber electrodes.…”

mentioning

confidence: 92%

Kinetic Study of Electrochemical Treatment of Carbon Fiber Microelectrodes Leading to In Situ Enhancement of Vanadium Flow Battery Efficiency

Miller

Bourke

Quill

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

Novel carbon fiber microelectrode (CFME) and flow cell experiments were used to investigate electrode treatments for vanadium flow batteries (VFBs). Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) on CFMEs showed that electrode treatments at positive potentials enhance the kinetics of V 2+ /V 3+ and inhibit the kinetics of VO 2+ /VO 2 + , while electrode treatments at negative potentials inhibit the kinetics of V 2+ /V 3+ and enhance the kinetics of VO 2+ /VO 2 + . XPS analysis showed changes in oxygen-containing species on electrode surfaces after treatment, supporting the suggestion that such species are responsible for the observed effects. The kinetics of VO 2+ /VO 2 + are significantly faster than that of V 2+ /V 3+ . Based on the CFME results, the range of potential experienced by a negative electrode in a flow cell during operation corresponds to a region where it is being deactivated by reduction, and the redox potential of the positive half-cell falls in a region where the electrode is activated for the V 2+ /V 3+ reaction. This is supported by flow cell experiments which showed that the overpotential at the negative electrode increases with charge-discharge cycling but decreases significantly when the positive and negative electrolytes are interchanged. The all-vanadium flow battery (VFB) has received attention as a load leveling technology for large-scale energy storage.1-4 This technology is capable of interfacing with renewable energy sources and provides an alternative solution to balancing power consumption and generation. Despite the advantages, VFBs have not yet been widely commercialized. Significant improvements are needed to enhance flow battery systems. Limitations include ion transport through the membrane, mass transport resistances within the electrodes, and electrode reaction kinetics. 5 Recently, attention has been directed toward improvement of electrochemical properties of carbon based electrode materials. Modifications via thermal treatments, chemical oxidation, or electrochemical oxidation are thought to enhance electrochemical activity.6-12 The presence of oxygen containing functional groups has been shown to directly affect the kinetics; surface oxides resulting from the aforementioned treatments are thought to act as active sites, catalyzing the vanadium reactions.13 Some researchers have reported an increase [6][7][8][9][10][11][12] while others reported a decrease 14 in activity upon functionalization of carbon electrodes. Many of these studies have been conducted using glassy carbon, 15,16 graphite, 17 carbon paper, 18 multi-walled carbon nanotubes, 19 or carbon composites. 20 One group concluded that the kinetics for the VO 2+ /VO 2 + reaction are faster than the V 2+ /V 3+ reaction at a plastic formed carbon electrode, but found the opposite when using pyrolytic graphite. 21 Previously, we reported that electrochemical oxidation treatments enhanced the V 2+ /V 3+ reaction kinetics, whereas electrochemical reduction treatments enhanced the VO 2...

show abstract

“…The kinetics of both the V II /V III and V IV /V V redox couples have been studied for a range of different carbon materials using a variety of techniques and it is clear that the kinetic rates depend strongly both on the type of carbon used and on the preparation of the electrode surface. 31,[35][36][37][38] Generally, the kinetics are found to be faster for V IV [17][18][19]21 and inhibition of V IV /V V electrode kinetics 17-21 by anodic treatment. In this paper we report detailed results on the effects of both anodic and cathodic treatment on the kinetics of the V IV /V V couple at carbon electrodes (glassy carbon, graphite, carbon paper, reticulated vitreous carbon (RVC), and carbon fibers).…”

mentioning

confidence: 99%

Effect of Cathodic and Anodic Treatments of Carbon on the Electrode Kinetics of V^IV/V^VOxidation-Reduction

Bourke¹,

Miller²,

Lynch³

et al. 2015

J. Electrochem. Soc.

View full text Add to dashboard Cite

Cyclic voltammetry and electrochemical impedance spectroscopy were used to examine several types of carbon electrodes in V IV /V V in H 2 SO 4 . The materials investigated included glassy carbon, graphite, carbon paper, reticulated vitreous carbon and carbon fibers. In all cases the electrode kinetics of the V IV /V V oxidation-reduction reactions are enhanced by cathodic treatment of the electrode and inhibited by anodic treatment. Pronounced activation typically occurs at potentials more negative than +0.1 V (vs. Hg/Hg 2 SO 4 ); the effect begins to saturate at about -0.6 V. Pronounced deactivation typically occurs at potentials more positive than +0.7 V. Both activation and deactivation occur rapidly during the first ∼10 s at the most negative and most positive potentials, respectively. The activation effect saturates quickly at the most negative potentials but the deactivation effect does not saturate on the time scales investigated. There is a considerable shift (∼1.1 V) between the potentials for activation and deactivation. Activated electrodes showed no significant loss of activity after standing in the electrolyte for 3 weeks; deactivated electrodes regained about 50% of their activity. The activation and deactivation effects were observed regardless of whether vanadium was present in the electrolyte and are attributed to oxygen-containing functional groups on the electrode surface. All-Vanadium Flow Batteries (VFBs) are a promising technology to meet energy storage requirements for large scale and remote area applications.1-6 Like other flow battery systems the VFB is an electrochemical device that converts electrical energy to chemical energy which is stored in the electrolyte. Typical cells have carbon felt electrodes separated by a proton exchange membrane. The catholyte and the anolyte are circulated through the electrodes from reservoirs. Both electrolytes are highly acidic, typically 3 mol dm A variety of electrode treatments have been reported, including electrochemical, 17-28 chemical, 22,23,27,29,30 and thermal 31-34 treatments. These treatments often have the effect of oxidizing or reducing the surface and the influence of surface oxygen species on the performance of carbon electrodes is recognized, 50-53 although often not well understood.In order to better understand and improve the performance of VFB electrodes, it is important to investigate the electrode kinetics. The kinetics of both the V II /V III and V IV /V V redox couples have been studied for a range of different carbon materials using a variety of techniques and it is clear that the kinetic rates depend strongly both on the type of carbon used and on the preparation of the electrode surface. 31,[35][36][37][38] Generally, the kinetics are found to be faster for V IV [17][18][19]21 and inhibition of V IV /V V electrode kinetics 17-21 by anodic treatment. In this paper we report detailed results on the effects of both anodic and cathodic treatment on the kinetics of the V IV /V V couple at carbon electrodes (glassy carbon, gra...

show abstract

Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes

Cited by 210 publications

References 45 publications

A three-dimensional model for negative half cell of the vanadium redox flow battery

A three-dimensional model for negative half cell of the vanadium redox flow battery

Kinetic Study of Electrochemical Treatment of Carbon Fiber Microelectrodes Leading to In Situ Enhancement of Vanadium Flow Battery Efficiency

Effect of Cathodic and Anodic Treatments of Carbon on the Electrode Kinetics of V^IV/V^VOxidation-Reduction

Contact Info

Product

Resources

About

Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes

Cited by 210 publications

References 45 publications

A three-dimensional model for negative half cell of the vanadium redox flow battery

A three-dimensional model for negative half cell of the vanadium redox flow battery

Kinetic Study of Electrochemical Treatment of Carbon Fiber Microelectrodes Leading to In Situ Enhancement of Vanadium Flow Battery Efficiency

Effect of Cathodic and Anodic Treatments of Carbon on the Electrode Kinetics of VIV/VVOxidation-Reduction

Contact Info

Product

Resources

About

Effect of Cathodic and Anodic Treatments of Carbon on the Electrode Kinetics of V^IV/V^VOxidation-Reduction