Species transport mechanisms governing capacity loss in vanadium flow batteries: Comparing Nafion® and sulfonated Radel membranes

Ağar, Ertan; Knehr, Kevin W.; Chen, Dongyang; Hickner, Michael A.; Kumbur, E. Caglan

doi:10.1016/j.electacta.2013.03.030

Cited by 116 publications

(79 citation statements)

References 37 publications

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“…Figures 8c-8d show the relative contributions of diffusion, convection, and migration to the total flux of V 5+ and V 4+ during charging. As expected from previous studies, 26,28 the transport in this system is dominated by diffusion. This diffusion dominance is believed to contribute to the asymptotic behavior seen in Figure 8a.…”

Section: Resultssupporting

confidence: 89%

“…So far, there are several studies reported that have focused on investigating the change in long-term performance of VRFBs based on vanadium crossover across the membrane. [22][23][24][25][26][27][28][29] The early attempts were made by Syllas-Kazacos and her co-workers. They developed a zero-dimensional, transient model including vanadium diffusion across the membrane to predict the energy capacity during cycling.…”

mentioning

confidence: 99%

“…More detailed information about the model including governing equations, initial and boundary conditions, and constant parameters can be found in our group's earlier studies. 22,26,28 …”

mentioning

confidence: 99%

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Modeling of Ion Crossover in Vanadium Redox Flow Batteries: A Computationally-Efficient Lumped Parameter Approach for Extended Cycling

Boettcher

Ağar

Dennison

et al. 2015

J. Electrochem. Soc.

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In this work, we have developed a zero-dimensional vanadium redox flow battery (VRFB) model which accounts for all modes of vanadium crossover and enables prediction of long-term performance of the system in a computationally-efficient manner. Using this model, the effects of membrane thickness on a 1000-cycle operation of a VRFB system have been investigated. It was observed that utilizing a thicker membrane significantly reduces the rate of capacity fade over time (up to ∼15%) at the expense of reducing the energy efficiency (up to ∼2%) due to increased ohmic losses. During extended cycling, the capacity of each simulated case was observed to approach an asymptote of ∼60% relative capacity, as the concentrations in each half-cell reach a quasi-equilibrium state. Simulations also indicated that peak power density and limiting current density exhibit a similar asymptotic trend during extended cycling (i.e., an ∼10-15% decrease in the peak power density and an ∼20-25% decrease in the limiting current density is observed as quasi-equilibrium state is reached Recently, vanadium redox flow batteries (VRFBs) have gained significant interest as one of the most promising electrochemical systems for grid-scale energy storage due to their several advantages over conventional batteries.1,2 Among these advantages, the most important ones are their ability to decouple power and energy rating due to their unique system architecture, and their flexible design.3-6 Despite these advantages, one major challenge which hinders their commercial viability is the relatively higher capital cost of these systems.5 According to a recent study by Pacific Northwest National Laboratory, the current capital cost of a VRFB system is about $350 per kWh for 4-h application, 7 which is much higher than the capital cost target set by government agencies. The current capital cost target of The Department of Energy's Office of Electricity Delivery and Energy Reliability is $250 per kWh, falling to $150 per kWh in the future for a 4-hour energy storage system. 8 One possible approach to reduce the capital cost is to improve the performance of these systems for less material use. To date, the majority of research has focused on improving the performance of individual components, such as developing high power density electrodes 4,[9][10][11][12][13][14][15][16] and exploring high energy capacity electrolytes. [17][18][19][20][21] In line with these studies, another approach to reduce the capital cost is to increase the lifetime of VRFB systems. Currently, the lifetime of these systems is limited by the capacity fade during cycling, which is primarily governed by unwanted active species transport across the membrane (i.e., species crossover). 22 Developing sophisticated mathematical models to mimic the VRFB operation is imperative to investigate the capacity fade and related performance losses in these systems due to lengthy time requirements and practical limitations of experimental cycling analysis. So far, there are several studies reported that ha...

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Section: Resultssupporting

confidence: 89%

mentioning

confidence: 99%

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Modeling of Ion Crossover in Vanadium Redox Flow Batteries: A Computationally-Efficient Lumped Parameter Approach for Extended Cycling

Boettcher

Ağar

Dennison

et al. 2015

J. Electrochem. Soc.

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“…It was observed that at the end of cycling a specific amount of negative electrolyte had moved through the membrane to the positive cell compartment, suggesting that the crossover is the cause of the loss in ve 34 . The vanadium ion crossover in Nafion® membranes was described earlier by other groups 35,36 . Agar et al reported that the transport in Nafion® membranes is governed by a diffusion process 36 .…”

Section: Membrane Performance In a Vrfbmentioning

confidence: 82%

Stability of acid-excess acid–base blend membranes in all-vanadium redox-flow batteries

Chromik

Santos

Turek

et al. 2015

Journal of Membrane Science

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“…10b. The capacity loss occurs primarily due to the undesired transport of active vanadium species across the membrane during operation [29]. All VRSBs show declined capacity retention, but the VRSBs with SPI membranes display higher capacity retention especially for SPI (BAPP) and SPI (APABI) because of their excellent vanadium resistance property.…”

Section: Vrsb and Vrfb Cyclic Studiesmentioning

confidence: 99%

Sulfonated polyimide membranes with different non-sulfonated diamines for vanadium redox battery applications

Zhang

et al. 2014

Electrochimica Acta

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Species transport mechanisms governing capacity loss in vanadium flow batteries: Comparing Nafion® and sulfonated Radel membranes

Cited by 116 publications

References 37 publications

Modeling of Ion Crossover in Vanadium Redox Flow Batteries: A Computationally-Efficient Lumped Parameter Approach for Extended Cycling

Modeling of Ion Crossover in Vanadium Redox Flow Batteries: A Computationally-Efficient Lumped Parameter Approach for Extended Cycling

Stability of acid-excess acid–base blend membranes in all-vanadium redox-flow batteries

Sulfonated polyimide membranes with different non-sulfonated diamines for vanadium redox battery applications

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