• Journal of Hydrogen and New Energy
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• v.26 no.2
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• pp.170-178
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• 2015

In this study, we carry out a study on how to improve performance of vanadium redox flow battery (VRFB) through promoting reaction rate of rate determining vanadium reaction ($[VO]^{2+}/[VO_2]^+$). In order to do that, three different carbons like Vulcan (XC-72), CMK3 and MSU-F-C are adopted as the catalysts, while their catalytic activity and reaction reversibility are evaluated using half-cell tests. Their topological images are also measured by TEM. For estimation of the VRFB performance, multiple charge-discharge curves of VRFBs including the catalysts are measured by single cell tests. As a result of that, MSU-F-C shows relatively excellent catalytic activity and reaction reversibility as well as large surface area compared to those of Vulcan (XC-72) and CMK3. Also, in terms of the performance of VRFBs including the catalysts, VRFB including MSU-F-C indicates (i) low charging/discharging overpotentials and low internal resistance, (ii) high charge/discharge capacities and (iii) high energy efficiency. These VRFB performance data are well agreed with results on catalytic activity and reaction reversibility. The reason that MSU-F-C induces superior VRFB performances is attributed to (i) its large surface area and (ii) its hydrophilic surface functional groups that mainly consist of hydroxyl bonds that are supposed to play active surface site role for facilitaing $[VO]^{2+}/[VO_2]^+$ redox reaction. Based on the above results, it is found that adoption of MSU-F-C as catalyst for VRFB results in improvement in VRFB performance by promoting the languid $[VO]^{2+}/[VO_2]^+$ redox reaction.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.847-852
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• 2019

In this study, the effect of additives on the performance of aqueous organic redox flow battery (AORFB) using quinoxaline and ferrocyanide as active materials in alkaline supporting electrolyte is investigated. Quinoxaline shows the lowest redox potential (-0.97 V) in KOH supporting electrolyte, while when quinoxaline and ferrocyanide are used as the target active materials, the cell voltage of this redox combination is 1.3 V. When the single cell tests of AORFBs using 0.1 M active materials in 1 M KCl supporting electrolyte and Nafion 117 membrane are implemented, it does not work properly because of the side reaction of quinoxaline. To reduce or prevent the side reaction of quinoxaline, the two types of additives are considered. They are the potassium sulfate as electrophile additive and potassium iodide as nucleophilie additive. Of them, when the single cell tests of AORFBs using potassium iodide as additive dissolved in quinoxaline solution are performed, the capacity loss rate is reduced to $0.21Ah{\cdot}L^{-1}per\;cycle$ and it is better than that of the single cell test of AORFB operated without additive ($0.29Ah{\cdot}L^{-1}per\;cycle$).

• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.890-894
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• 2018

In this study, methylene blue which is one of dye materials was introduced as active material for aqueous redox flow battery. The redox potential of methylene blue was shifted to negative direction as pH increased. The full-cell performance was evaluated by using methylene blue as the negative active material and vanadium as the positive active material with acid supporting electrolytes. The cell voltage of methylene $blue/V^{4+}$ is very low (0.45 V). In addition, the maximum solubility of methylene blue in water is only 0.12 M. Therefore, the cell test was performed with very low concentration (0.0015 M methylene blue, $0.15M\;V^{4+}$) at first time. Cut-off voltage range was 0 to 0.8 V and $1mA{\cdot}cm^{-2}$ current density was adopted during cycling. As a result, current efficiency (CE) was 99.67%, voltage efficiency (VE), 88.83% and energy efficiency (EE) was 85.87% and discharge capacity was ($0.0500Ah{\cdot}L^{-1}$) at 4 cycle. In addition, the cell test was performed with increased concentration (0.1 M methylene blue, $0.15M\;V^{4+}$) with $10mA{\cdot}cm^{-2}$ current density, leading to higher discharge capacity ($3.8122Ah{\cdot}L^{-1}$) with similar efficiency (CE=99%, VE=85%, EE=85% at 4 cycle).

• Journal of the Korean Electrochemical Society
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• v.17 no.2
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• pp.94-102
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• 2014

Cation exchange membrane (Nafion) was modified to reduce the vanadium ion permeation through the membrane and to increase the vanadium redox flow battery (VRB) system performance by coating the graphene oxide (GO) which has nano-plate like morphology. Modified membrane properties were studied by measuring the ion exchange capacity (I.E.C), water uptake and proton conductivity. The thickness of the coated layer on the surface of the Nafion membrane was observed as $0.93{\mu}m$ by SEM. Proton conductivity and vanadium ion permeability of the modified membrane were decreased to 27% and 25% compared to that of the commercial Nafion membrane respectively. VRB single cell performance test was performed to compare the system performance of the VRB applied with commercial Nafion membrane and modified membrane. VRB system applied with modified membrane showed higher coulombic efficiency and energy efficiency than the VRB system applied with the commercial Nafion membrane due to the reduction of the vanadium ion permeation. From these result, we could suggest that the membrane modification by coating the GO on the surface of the Nafion membrane could be one of the promising strategies to reduce the vanadium ion permeation and to increase the VRB system performance effectively.

• 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.

• 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.

• Composites Research
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• v.34 no.3
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• pp.148-154
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• 2021

Carbon/epoxy composite bipolar plate (BP) is a BP that is likely to replace existing graphite bipolar plate of vanadium redox flow cell (VRFB) due to its high mechanical properties and productivity. Multi-functional carbon/epoxy composite BP requires graphite coating or additional surface treatment to reduce interfacial contact resistance (ICR). However, the expanded graphite coating has the disadvantage of having low durability under VRFB operating conditions, and the surface treatments incur additional costs. In this work, an excessive resin absorption method is developed, which uniformly removes the resin rich area on the surface of the BP to expose carbon fibers by applying polyester fabric. This method not only reduces ICR by exposing carbon fibers to BP surfaces, but also forms a unique ditch pattern that can effectively hold carbon felt electrodes in place. The acidic environmental durability, mechanical properties, and gas permeability of the developed carbon/epoxy composite BP are experimentally verified.

• Composites Research
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• v.36 no.6
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• pp.422-428
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• 2023

The electrical contact resistance between the bipolar plate (BP) and the carbon felt electrode (CFE), which are in contact by the stack clamping pressure, has a great impact on the stack efficiency because of the relatively low clamping pressure of the vanadium redox flow battery (VRFB) stack. In this study, a polyethylene (PE) composite-CFE hybrid bipolar plate structure is developed through a local heat welding process to reduce such contact resistance and improve cell performance. The PE matrix of the carbon fiber composite BP is locally melted to create a direct contact structure between the carbon fibers of CFE and the carbon fibers of BP, thereby reducing the electrical contact resistance. Area specific resistance (ASR) and gas permeability are measured to evaluate the performance of the PE composite-CFE hybrid bipolar plate. In addition, an acid aging test is performed to measure stack reliability. Finally, a VFRB unit cell charge/discharge test is performed to compare and analyze the performance of the developed PE composite-CFE hybrid BP and the conventional BP.

• International Journal of Naval Architecture and Ocean Engineering
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• v.13 no.1
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• pp.674-690
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• 2021

This study proposes a hybrid marine power system combining dual-fuel generators, a fuel cell, and Vanadium Redox Flow Batteries (VRFB). Rigorous verification and validation of the dynamic modelling and integration of the system are conducted. A case study for the application of the hybrid propulsion system to a passenger ship is conducted to examine its time-variant behaviour. A comprehensive model of the reversible and irreversible capacity degradation of the VRFB stack unit is proposed and validated. The capacity retention of the VRFB stack is simulated by being integrated within the hybrid propulsion system. Reversible degradation of the VRFB stack is precisely predicted and rehabilitated based on the predefined operational schedule, while the irreversible portion is retained until the affected components are replaced. Consequently, the advantages of the VRFB system as an on-board ESS are demonstrated through the application of a hybrid propulsion system for liner shipping with fixed routes.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.175.2-175.2
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• 2011

바나듐 3, 4, 5가 이온은 공기 중에서 안정하지만, 바나듐 2가 이온은 쉽게 산화된다. 그러므로 바나듐 2가 이온이 담겨져 있는 음극 탱크가 공기와 접촉하지 않게 하는 것이 중요하다. 충전 중 음극 탱크에 공기가 침투되면, 바나듐 2가 이온은 3가 이온으로 산화되기 때문에 음극과 양극의 전해질에 불균형을 초래한다. 이러한 불균형은 바나듐 레독스 흐름전지 용량저하의 원인이 된다. 본 연구에서는 공기 중 2가 이온 산화에 의한 전해질의 불균형 현상을 쉽게 보여주기 위해, 공기노출과 차단조건에서 충방전 중에 발생한 음극과 양극의 바나듐 이온 상태변화량을 UV-Visible spectrophotometer를 이용해 정량적으로 분석하였다. 분석 결과, 공기노출 조건에서 음극의 충전 시, 충방전 cycle이 진행 될수록 바나듐 2가 이온의 양이 현격히 줄어들었지만, 공기차단 조건에서는 2가 이온의 양이 공기노출 조건보다 훨씬 더 적게 줄어들었다. 즉, 공기차단 조건에서는 바나듐 2가 이온이 3가로 산화되지 않아서 음극의 충전 후 바나듐 3가에서 2가로 전환되는 양이 공기노출 조건보다 더 많은 것을 확인할 수 있었다. 이러한 영향으로 인해, 충방전 10th cycle을 진행해 본 결과, 공기차단 조건에서는 충방전 용량감소가 거의 없었지만 공기노출 조건에서는 현격한 충방전 용량 감소를 보였다.