• Journal of Electrochemical Science and Technology
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• v.14 no.2
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• pp.152-161
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• 2023

Vanadium redox flow batteries (VRFBs) have been considered one of promising power sources for large scale energy storage systems (ESS) because of their excellent cycle performance and good safety. However, VRFBs still have a few challenging issues, such as poor Coulombic efficiency due to vanadium crossover between catholyte and anolyte, although recent efforts have shown promise in electrochemical performance. Herein, the vanadium complexes with various glyme ligands have been examined as active materials to suppress vanadium crossover between catholyte and anolyte, thus improving the Coulombic efficiency of VRFBs. The conventional Nafion membrane has a channel size of ca. 10 Å, whereas vanadium cation species are small compared to the Nafion membrane channel. For this reason, vanadium cations can permeate through the Nafion membrane, resulting in significant vanadium crossover during cycling, although the Nafion membrane is a kind of ion-selective membrane. In this regard, various glyme additives, such as 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), and tetraethylene glycol dimethyl ether (tetraglyme) have been examined as complexing agents for vanadium cations to increase the size of vanadium-ligand complexes in electrolytes. Since the size of vanadium-glyme complexes is proportional to the chain length of glymes, the vanadium permeability of the Nafion membrane decreases with increasing the chain length of glymes. As a result, the vanadium complexes with tetraglyme shows the excellent electrochemical performance of VRFBs, such as stable capacity retention (90.4% after 100 cycles) and high Coulombic efficiency (98.2% over 100 cycles).

• Advances in Energy Research
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• v.4 no.4
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• pp.285-297
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• 2016

Fundamental understanding of vanadium ion transport and the detrimental effects of cross-contamination on vanadium redox flow battery (VRFB) performance is critical for developing low-cost, robust, and highly selective proton-conducting membranes for VRFBs. The objective of this work is to examine the effect of conductivity and diffusivity, two key membrane parameters, on long-cycle performance of a VRFB at different operating conditions using a transient 2D multi-component model. This single-channel model combines the transport of vanadium ions, chemical reactions between permeated ions, and electrochemical reactions. It has been discovered that membrane selecting criterion for long cycles depends critically on current density and operating voltage range of the cell. The conducted simulation work is also designed to study the synergistic effects of the membrane properties on dynamics of VRFBs as well as to provide general guidelines for future membrane material development.

• Korean Chemical Engineering Research
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• v.56 no.1
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• pp.24-28
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• 2018

The redox flow battery (RFB) is a large-capacity energy storage equipment, and the vanadium redox flow cell is a typical RFB, but VRFB is expensive. Iron-chrome RFBs are economical because they use low-cost active materials, but their low performance is a urgent problem. In this study, the crossover of iron and chromium ion through Nafion membrane and the stability of Nafion membrane in HCl solution were investigated. The permeability of iron and chrome ion through Nafion were $5.5{\times}10^{-5}$ and $6.0{\times}10^{-5}cm^2/min$, respectively, which was 18.9~20.7 times higher than that of vanadium ion ($2.9{\times}10^{-6}cm^2/min$). The crossover of iron and chromium ions were shown to be a cause of performance decrease in Iron-chrome RFB. As the temperature increases, the crossover increases rapidly (activation energy 38.8 kJ/ mol), indicating that operation at low temperature is a methode to reduce the performance loss due to crossover. Nafion membranes were relatively stable in 3 M HCl solution.

• Membrane Journal
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• v.30 no.1
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• pp.21-29
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• 2020

In this study, we have established the optimum design condition of pore-filled anion-exchange membrane for all-vanadium redox flow battery (VRFB). From the experimental results, it was proven that the membrane design factors that have the greatest influence on the charge-discharge performance of VRFB are the ion exchange capacity, the porosity of substrate film, and the crosslinking degree. That is, the ohmic loss and the crossover of active materials in VRFB were shown to be determined by the above factors. In addition, two methods, i.e. reducing the ion exchange capacity at low crosslinking degree and increasing the crosslinking degree at high ion exchange capacity, were investigated in the preparation of pore-filled anion-exchange membranes. As a result, it was found that optimizing the crosslinking degree at sufficiently high ion exchange capacity is more desirable to achieving high VRFB charge-discharge performances.

• Membrane Journal
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• v.30 no.5
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• pp.307-318
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• 2020

Conventional perfluorinated sulfonic acid membrane, Nafion is widely used for vanadium redox flow battery (VRFB). It is desired to prevent vanadium ion permeation through a membrane to retain the capacity, and to keep the cell efficiency of a VRFB. Highly proton conductive and chemically stable Nafion membranes, however, suffer from high vanadium permeation, which induce the reduction in charge and discharge capacity by side reactions of vanadium ions. In this study, to resolve the issue, silica nanoparticles, which are functionalized with 3-aminopropyl group (fS) are introduced to enhance the long-term performance of a VRFB by lowering vanadium permeation. It is expected that amine groups on silica nanoparticles are converted to positive ammonium ion, which could deteriorate positively charged vanadium ions' crossover by Gibbs-Donnan effect. There is reduction in proton conductivity may due to acid-base complexation between fS and Nafion side chains, but ion selectivity of proton to vanadium ion is enhanced by introducing fS to Nafion membranes. With the composite membranes of Nafion and fS, VRFBs maintain their discharge capacity up to 80% at a high current density of 150 mA/㎠ during 200 cycles.

• Korean Chemical Engineering Research
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• v.57 no.1
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• pp.17-21
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• 2019

The redox flow battery (RFB) is a large-capacity energy storage equipment, and the vanadium redox flow cell is a typical RFB, but VRFB is expensive. Iron-chrome RFBs are economical because they use low-cost active materials, but their low performance is an urgent problem. One of the reasons for the low performance is the crossover of the active materials. In this study, the sulfonated Poly (ether ether ketone) (sPEEK) membrane, which is a hydrocarbon membrane, was used instead of the fluorine membrane to reduce the crossover of the active materials. The chromium ion permeability of the sPEEK membrane was $1.8{\times}10^{-6}cm^2/min$, which was about 1/33 of that of the Nafion membrane. Thus, it was shown that the use of the sPEEK membrane instead of the fluorine membrane could solve the high active material crossover problem. The activation energy of iron diffusion through the sPEEK membrane was 24.9 kJ/mol, which was about 66% of Nafion membrane. And that the e-PTFE support in the polymer membrane reduces the active material crossover through Iron-Chrome Redox Flow Battery (ICRFB).

• Journal of the Korean Electrochemical Society
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• v.19 no.1
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• pp.21-27
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• 2016

Vanadium redox flow batteries (VRFBs) using the electrolytes containing various vanadium ions in sulfuric acid as supporting solution are one of the energy storage devices in alternatively charging and discharging operation modes. The positive electrolyte contains $V^{5+}/V^{4+}$ and the negative electrolyte $V^{2+}/V^{3+}$ depending on the operation mode. To prevent the mixing of two solutions, proton exchange membranes are mainly used in VRFBs. Nafion 117 could be the most promising candidate due to the strong oxidative property of $V^{5+}$ ion, but causes high crossover of electroactive species to result in a decrease in coulombic efficiency. In this study, the composite membranes using Nafion ionomer and porous polyethylene substrate were prepared to keep good chemical stability and to decrease the cost of membranes, and were compared to the properties and performance of the commercially available electrolyte membrane, Nafion 117. As a result, the water uptake and ionic conductivity of the composite membranes increased as the thickness of the composite membranes increased, but those of Nafion 117 slightly decreased. The permeability of vanadium ions for the composite membranes significantly decreased compared to that for Nafion 117. In a single cell test for the composite membranes, the voltage efficiency decreased and the coulombic efficiency increased, finally resulting in the similar energy efficiency. In conclusion, the less cost of the composite membranes by decreasing 6.4 wt.% of the amount of perfluorinated sulfonic acid polymer due to the introduction of porous substrate and lower vanadium ion permeability to decrease self-discharge were achieved than Nafion 117.

• Journal of ILASS-Korea
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• v.22 no.2
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• pp.69-79
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• 2017

When designing a redox flow battery system, compression of battery stack is required to prevent leakage of electrolyte and to reduce contact resistance between cell components. In addition, stack compression leads to deformation of the porous carbon electrode, which results in lower porosity and smaller cross-sectional area for electrolyte flow. In this paper, we investigate the effects of electrode compression on the cell performance by applying multi-dimensional, transient model of all-vanadium redox flow battery (VRFB). Simulation result reveals that large compression leads to greater pressure drop throughout the electrodes, which requires large pumping power to circulate electrolyte while lowered ohmic resistance results in better power capability of the battery. Also, cell compression results in imbalance between anolyte and catholyte and convective crossover of vanadium ions through the separator due to large pressure difference between negative and positive electrodes. Although it is predicted that the battery power is quickly improved due to the reduced ohmic resistance, the capacity decay of the battery is accelerated in the long term operation when the battery cell is compressed. Therefore, it is important to optimize the battery performance by taking trade-off between power and capacity when designing VRFB system.