• Analytical Science and Technology
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• v.28 no.5
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• pp.341-346
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• 2015

In order to understand the counter anionic effects in a non-aqueous vanadium redox flow battery (VRFB), we synthesized four types of electrolyte salts (1-ethyltriethamine tertafluoroborate, [E-TEDA]⁺[BF₄]⁻, 1-ethyltriethamine hexafluorophosphate, [E-TEDA]⁺[PF₆]⁻, 1-butyltriethylamine tertafluoroborate, [B-TEDA]⁺[BF₄]⁻, and 1-buthyltriethamine hexafluorophosphate [B-TEDA]⁺[PF₆]⁻) by counter anion exchange reaction after the SN₂ reaction. We confirmed the successful synthesis of the electrolyte salts [E-TEDA]⁺[Br]⁻ and [B-TEDA]⁺[Br]⁻ via ¹H-NMR spectroscopy and GC-mass analysis before the counter anion exchange reaction. The electric potential of the vanadium acetylacetonate, V(acac)₃, as an energy storage chemical was shown to be 2.2 V in the acetonitrile solvent with each of the [E-TEDA]⁺[BF₄]⁻, [E-TEDA]⁺[PF₆]⁻, [B-TEDA]⁺[BF₄]⁻, and [B-TEDA]⁺[PF₆]⁻ electrolyte salts. In a non-aqueous VRFB with a commercial Neosepta AFN membrane, the maximum voltages reached 1.0 V and 1.5 V under a fixed current value of 0.1 mA in acetonitrile with the [E-TEDA]⁺[BF₄]⁻ and [E-TEDA]⁺[PF₆]⁻ electrolyte salts, respectively. The maximum voltage was 0.8 V and 1.1 V under a fixed current value of 0.1 mA in acetonitrile with the [B-TEDA]⁺[BF₄]⁻ and [B-TEDA]⁺[PF₆]⁻ electrolyte salts, respectively. From these results, we concluded that in the non-aqueous VRFB more of the [PF₆]⁻ counter anion than the [BF₄]⁻ counter anion was transported onto the commercial Neosepta AFN anion exchange membrane.

• Korean Chemical Engineering Research
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• v.53 no.5
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• pp.638-645
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• 2015

Vanadium redox flow batteries (VRFBs) have been investigated for their potential utility as large energy storage systems due to their advantageous performances in terms of long cycle life, high energy efficiency, low cost, and flexible design. Carbon materials are typically used as electrodes in redox reactions and as a liquid electrolyte support. The activities, surface areas, and surface morphologies of porous carbon materials must be optimized to increase the redox flow battery performance. Here, to reduce the resistance in VRFBs, surface-modified carbon felt electrodes were fabricated, and their structural, morphological, and chemical properties were characterized. The surface-modified carbon felt electrode improved the cycling energy efficiencies in the VRFBs, from 65% to 73%, due to the improved wettability with electrolyte. From the results of impedances analysis with proposed fitting model, the electrolyte-coupled polarization in VRFB dramatically decreased upon modification of carbon felt electrode surface. It is also demonstrated that the compressibility of carbon felt electrodes was important to the VRFB polarization, which are concerned with mass transfer polarization. The impedance analysis will be helpful for obtaining better and longer-lived VRFB performances.

• Resources Recycling
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• v.31 no.2
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• pp.20-32
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• 2022

This study implemented a chelating agent (Ethylenediaminetetraacetic acid, EDTA) in purification to obtain high-purity vanadium pentoxide (V₂O₅) for use in VRFB (Vanadium Redox Flow Battery). V₂O₅ (powder) was produced through the precipitation recovery of ammonium metavanadate (NH₄VO₃) from a vanadium solution, which was prepared using a low-purity vanadium raw material. The initial purity of the powder was estimated to be 99.7%. However, the use of a chelating agent improved its purity up to 99.9% or higher. It was conjectured that the added chelating agent reacted with the impurity ions to form a complex, stabilizing them. This improved the selectivity for vanadium in the recovery process. However, the prepared V₂O₅ powder exhibited higher contents of K, Mn, Fe, Na, and Al than those in the standard counterparts, thus necessitating additional research on its impurity separation. Furthermore, the vanadium electrolyte was prepared using the high-purity V₂O₅ powder in a newly developed direct electrolytic process. Its analytical properties were compared with those of commercial electrolytes. Owing to the high concentration of the K, Ca, Na, Al, Mg, and Si impurities in the produced vanadium electrolyte, the purity was analyzed to be 99.97%, lower than those (99.98%) of its commercial counterparts. Thus, further research on optimizing the high-purity V₂O₅ powder and electrolyte manufacturing processes may yield a process capable of commercialization.

• Journal of the Korean Vacuum Society
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• v.9 no.1
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• pp.42-47
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• 2000

The amorphous vanadium oxide thin films for thin-film rechargeable lithium batteries were fabricated by r.f. reactive sputtering at room temperature. As the experimental parameter, oxygen partial pressure was varied during sputtering. At high oxygen partial pressures(>30%), the as-deposited films, constant current charge/discharge characteristics were carried out in 1M $LiPF_6$, EC:DMC+1:1 liquid electrolyte using lithium metal as anode. The specific capacity of amorphous $V_2O_5$ after 200cycles of operation at room temperature was higher compared to crystalline $V_2O_5$. The amorphous vanadium oxide thin film and crystalline film showed about 60$\mu$Ah/$\textrm{cm}^2\mu\textrm{m}$ and about 38$\mu$Ah/$\textrm{cm}^2\mu\textrm{m}$, respectively. These results suggest that the battery capacity of the thin film vanadium oxide cathode strongly depends on the crystallinity.

• 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.

• KEPCO Journal on Electric Power and Energy
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• v.7 no.2
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• pp.309-316
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• 2021

For the detection of the state of charge in VRFB-ESS, the analyses of UV-Visible spectrometry and the measurements of potential between the anolyte and catholyte were used in parallel. This paper includes the production of 4-valant ion from VOSO4 powder, 3- and 5-valant ions from electrochemical charge of 4-valant ion and 2-valant ion from 3-valant ion. It also includes the analyses of these valance ions and unknown electrolyte at any time using UV-Visible spectrometry. Through the analyses of the valance ions in samples, the SOCs of the samples at any charge-discharge times were verified.

• 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.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.40 no.12
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• pp.777-784
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• 2016

All-vanadium redox flow batteries (VRFBs) are used as energy storage systems for multiple intermittent power sources. The performance of the VRFBs depends on the materials and operating conditions. Hence, performance characterization is of great importance in the development of the VRFBs. This paper proposes a method for determining the maximum current density based on stoichiometric ratios. A laboratory-scaled VRFB with a projected electrode area of $25cm^2$ is electrically charged when the state of the charge has begun from 0.6. The operating conditions, such as current density and volumetric flow rate are important in the test, and the maximum current density is influenced by the mass transfer coefficient. The results show that increasing the electrolyte flow rate from 5 mL/min to 60 mL/min enhances the maximum current density up to $520mA/cm^2$.

• Journal of the Korean institute of surface engineering
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• v.30 no.2
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• pp.121-127
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• 1997

Vanadium tungsten oxide thin films were formed by RF magnetron sputtering and the effects of tungsten addition on the crystallinity and on the electrochemical behavior were investigated. X-ray analysis revealed that amorphized films could be obtained by tungase addition. In order to investigate the electrochemical behavior of the vanadium tungsten oxide films, electrochemical insertion and extraction of lithium were out in 1m $LiCIO_4$-PC-DME electrolyte using litium metal as a counter electrode. When the tungsten was added to the $V_2O_5$ films, cycling reversibility was considerably improved. Electrochemical test showed the cell capacity of about $70\mu\;Ah/\textrm{cm}^2-\mu\textrm{m}$ when the amount of additive tungseten reached 30 atomic percent. No appreciable degradation of the cell capacity could be observed after hundred cycles of insertion and extration od Li.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.40 no.12
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• pp.769-776
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• 2016

In this study, a numerical simulation of a vanadium redox flow battery was investigated for reactions involving an electrochemical species using comprehensive conservation laws and a kinetic model. For a 3-D geometry of the cell, the distributions of electric potential, vanadium concentration, overpotential, and ohmic loss were calculated. The cell temperature and initial vanadium ion concentration were set as variables. The voltage and electrochemical loss were calculated for each variable. The effects of each variable's impact on the electrochemical performance of a vanadium redox flow battery was numerically analyzed using the calculated overpotential in the electrode and the ohmic loss in the electrolyte phase. The cell temperature increased from $20^{\circ}C$ to $80^{\circ}C$ when the voltage efficiency decreased from 89.34% to 87.29%. The voltage efficiency increased from 88.65% to 89.25% when the vanadium concentration was changed from $1500mol/m^3$ to $3000mol/m^3$.