In-situ investigation of vanadium ion transport in redox flow battery

Luo, Qingtao; Li-yu, LI; Nie, Zimin; Wang, Wei; Wei, Xiaoliang; Li, Bin; Chen, Baowei; Yang, Zhenguo

doi:10.1016/j.jpowsour.2012.06.066

Cited by 76 publications

(51 citation statements)

References 19 publications

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“…[11,12] As cycling proceeds, more and more vanadium species are transferred from the negative to the positive half-cell, leading to an imbalance of active species in the positive and negative half-cells. In real charge-discharge cycling, the transfer rates of V 2 + and V 3 + are larger than those of VO 2 + and VO 2 + , thus resulting in the net transfer of vanadium species from the negative to the positive half-cell, which corroborates previously reported results.…”

Section: Resultsmentioning

confidence: 99%

“…[11] During the interdiffusion process, no current was applied to the VRB, and the driving force of ion transfer was only through the concentration gradient. Electrical neutrality of the positive and negative electrolytes was achieved mainly by the transfer of protons between the positive and negative half-cells.…”

Section: Resultsmentioning

confidence: 99%

“…[10] However, both the influence of the electric field on the transfer of vanadium ions [11] and drastic volume change [12] during real charge-discharge cycling have not been considered in the above modeling study, both of which have substantial impact on the VRB capacity behavior during cycling. Recent modeling results have suggested that differential crossover of vanadium ions across the membrane will give rise to capacity fading due to a build-up of vanadium ions in one half-cell with a corresponding decrease in the other.…”

Section: Introductionmentioning

confidence: 99%

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Capacity Decay and Remediation of Nafion‐based All‐Vanadium Redox Flow Batteries

Li²,

et al. 2012

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The relationship between electrochemical performance of vanadium redox flow batteries (VRBs) and electrolyte composition is investigated, and the reasons for capacity decay over charge-discharge cycling are analyzed and discussed herein. The results show that the reasons for capacity fading over real charge-discharge cycling include not only the imbalanced vanadium active species, but also the asymmetrical valence of vanadium ions in positive and negative electrolytes. The asymmetrical valence of vanadium ions leads to a state-of-charge (SOC)-range decrease in positive electrolytes and a SOC-range increase in negative electrolytes. As a result, the higher SOC range in negative half-cells further aggravates capacity fading by creating a higher overpotential and possible hydrogen evolution. Based on this finding, we developed two methods for restoring lost capacity, thereby enabling long-term operation of VRBs to be achieved without the substantial loss of energy resulting from periodic total remixing of electrolytes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Capacity Decay and Remediation of Nafion‐based All‐Vanadium Redox Flow Batteries

Li²,

et al. 2012

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“…Table S1 outlinest he capacity degradation during the early cycles in VRB operations reported by other groups. [13,23,24] In this case, the negative electrolyte is the limiting factor for the total VRB capacity. [13] Specifically,t he transfer rates of V 2 + and V 3 + are larger than those of VO 2 + and VO 2 + ,g iving rise to as teady decrease in the total amount of vanadium speciesi nt he negative electrolyte.…”

Section: Introductionmentioning

confidence: 99%

Capacity Decay Mitigation by Asymmetric Positive/Negative Electrolyte Volumes in Vanadium Redox Flow Batteries

Park

et al. 2016

ChemSusChem

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Capacity decay in vanadium redox flow batteries during charge-discharge cycling has become an important issue because it lowers the practical energy density of the battery. The battery capacity tends to drop rapidly within the first tens of cycles and then drops more gradually over subsequent cycles during long-term operation. This paper analyzes and discusses the reasons for this early capacity decay. The imbalanced crossover rate of vanadium species was found to remain high until the total difference in vanadium concentration between the positive and negative electrolytes reached almost 1 mol dm . To minimize the initial crossover imbalance, we introduced an asymmetric volume ratio between the positive and negative electrolytes during cell operation. Changing this ratio significantly reduced the capacity fading rate of the battery during the early cycles and improved its capacity retention at steady state. As an example, the practical energy density of the battery increased from 15.5 to 25.2 Wh L simply after reduction of the positive volume by 25 %.

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“…Luo and co-workers [4] measured vanadium ion transport in a redox flow battery using a mixed Vanadium/Fe system. In these experiments Vanadium redox couples (V +2 /V +3 or V +4 /V +5 ) were paired with the Fe +2 /Fe +3 redox couple to form a working flow battery cell.…”

Section: Vrb Cell Resultsmentioning

confidence: 99%

Direct Measurement of Vanadium Crossover in an Operating Vanadium Redox Flow Battery

Sing

Meyers

2013

ECS Trans.

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Measurements of Vanadium diffusion coefficients for transportacross cation exchange membranes using dialysis cells have beenreported in the literature. However, to date direct measurement ofcrossover coefficients in an operating Vanadium redox flowbattery (VRB) cell have not been reported. Results are reported inthis paper on experiments utilizing a special VRB cell whichallows measurement of Vanadium ion transport across ionexchange membranes with and without the presence of current.The cell utilizes two additional flow regions which collectVanadium ions which diffuse from the positive and negative halfcells. The effects of the magnitude and direction of electricalcurrent on transport can be measured directly with this cell. Weobserve that transport is greatly enhanced when the direction of thehydrogen ion flux is in the same direction as the density gradientdriven vanadium flux and suppressed when the hydrogen ion fluxis in the opposite direction. The cell has been used to of investigatethe effects on transport of current densities up to 900 mA/cm2.

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In-situ investigation of vanadium ion transport in redox flow battery

Cited by 76 publications

References 19 publications

Capacity Decay and Remediation of Nafion‐based All‐Vanadium Redox Flow Batteries

Capacity Decay and Remediation of Nafion‐based All‐Vanadium Redox Flow Batteries

Capacity Decay Mitigation by Asymmetric Positive/Negative Electrolyte Volumes in Vanadium Redox Flow Batteries

Direct Measurement of Vanadium Crossover in an Operating Vanadium Redox Flow Battery

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