Performance Of Redox Flow Battery Research Articles

Enhancement in the Performance of a Vanadium-Manganese Redox Flow Battery using Electrospun Carbon Metal-based Electrode Catalysts

This study investigates the performance of both a vanadium/manganese redox flow battery (V/Mn RFB) and an all-vanadium redox flow battery (VRFB), employing carbon metal fabrics (CMFs) prepared through electrospinning followed by carbonization. Noteworthy advancements are observed in both systems upon coupling CMFs with thermally treated graphite felt (GF) electrodes. Nearly doubled peak power density and 50% higher capacity utilization over 150 charge/discharge cycles at 75 mA cm−2 are achieved for the V/Mn RFB with the incorporation of CMFs alongside graphite felt as catalysts. The VRFB demonstrates notable enhancements too, achieving approximately 200 cycles at a current density of 80 mA cm−2, with high efficiencies (85%) and electrolyte utilization (79%) when CMFs are used in combination with graphite felts. These advancements may facilitate pilot-scale testing and integration of the V/Mn RFB for the employment in the renewable energy storage sector and grid-balancing studies.

Enhanced Vanadium Redox Flow Battery Performance with New Amphoteric Ion Exchange Membranes.

Vanadium redox flow batteries (VRFBs) depend on the separator membrane for their efficiency and cycle life. Herein, two amphoteric ion exchange membranes are synthesized, based on sulfonic acid group-grafted poly(p-terphenyl piperidinium), for VRFBs. Using ether-free poly(p-terphenyl piperidine) (PTP) as the polymer matrix, and sodium 2-bromoethanesulphonate (ES) and 1,4-butane sultone (BS) as grafting agents, We achieve quaternization of PTP through an environmentally friendly process without alkaline catalysts. PTP-ES and PTP-BS membranes exhibit low area resistance, high H+ permeability, and significantly reduced vanadium ion permeability, leading to exceptional ion selectivity, which is 3.06×106Smincm-3 and 4.34×106Smincm-3, respectively,three orders of magnitude higher than that of Nafion115 (0.27×104Smincm-3). The VRFB with PTP-BS achieves a self-discharge duration of 190h, compared to 86h for Nafion 115. Additionally, under current densities of 40-160mAcm-2, PTP-BS shows coulombic efficiencies of 98.1-99.1% and energy efficiencies of 92.0-82.1%, outperforming Nafion 115. The VRFB with PTP-BS also demonstrates excellent cycle stability and discharge capacity retention over 300 cycles at 100mAcm-2. Therefore, the amphoteric PTP-BS membrane shows remarkable performance, offering significant potential for VRFB applications.

Numerical and experimental study on fractal flow field for improving the performance of non-aqueous redox flow battery

The flow field design of the non-aqueous redox flow battery (RFB) decides the electrolyte flow and mass transfer of active species inside porous electrode, which has a significant influence on the operation of RFB. In this work, a fractal tree-like flow channel is proposed to enhance the electrolyte convection and optimize the concentration distribution of active species inside the graphite felt electrode, thus boosting the overall battery performance. Using the finite element simulation method, a three-dimensional numerical model of single cell is established to comparatively study the steady-state discharge process characteristics of deep eutectic solvent (DES) electrolyte-based vanadium‑iron RFBs with fractal and serpentine flow fields, respectively. Moreover, by assembling the single cell of this RFB and building the full cell test system, an experimental study is conducted to compare the discharging output voltage and power of the RFBs with serpentine flow field and fractal flow fields of different fractal dimensions. The numerical results show that the fractal tree-like flow field can improve the discharging power of RFB as well as reduce the pumping loss compared with the conventional serpentine flow field. That is mainly attributed to that fractal flow field is conducive to reducing the polarization loss and strengthening the convection in porous electrode simultaneously. What's more, the role of fractal dimension of flow field is also investigated numerically, thus knowing that large fractal dimension promotes lower pumping loss while small fractal dimension is in favor of higher output voltage. In addition, the experimental results also demonstrate that the fractal flow field could improve the output voltage and maximum discharging power of RFB compared to serpentine flow field. This work provides an optimization method for the flow field design of DES electrolyte-based vanadium‑iron RFB, and is expected to be employed in the other non-aqueous RFBs.

Hierarchical interconnected polyaniline nanocomposite with hydrothermally synthesized pyrite structure for improved electrochemical properties in a vanadium redox flow battery

In this study, FeS2 (FS) was synthesized via the hydrothermal technique. The various percentages of FS were subsequently incorporated into polyaniline (PANI) through an in-situ chemical process, aiming to improve the performance of the vanadium redox flow battery (VRFB). The synthesized nanocomposites (NPFS) were characterized using various techniques such as spectroscopy, microscopy, chemical, thermal study and electrochemical analysis (CV, EIS and Tafel) and charge discharge cycles study to understand their structure and performance. Morphological, chemical and structural analyses revealed the successful integration of FS into the PANI matrix, forming a hierarchical with highly porous nanocomposite structure. The results of the electrochemical analysis significantly improved the redox behavior and charge transfer kinetics compared to PANI. Based on the characterization and electrochemical characterizations, the best performing composition (NPFS15) sample (3 mg/cm2) was coated on 132 cm2 graphite felt (GF) and inserted in VRFB to examine the charge–discharge cycles. At a current density 70 mA/cm2, the selected nanocomposite with the specified loading on GF exhibited superior electrochemical performance due to the sufficient availability of active sites. Besides, the integration of NPFS nanocomposite materials in VRFB technology may pave the way for more efficient and sustainable energy storage solutions in the future.

Mitigation of Negative-Electrode Degradation in Vanadium Redox Flow Batteries

Electrode overpotentials are among the major factors that impact the performance of redox flow batteries (RFBs). However, even though the all-vanadium redox flow battery (VRFB) is the most mature flow-battery chemistry, a recent review article has pointed out that “there is poor agreement between the reported values of kinetic parameters” [1]. Major contributors to this disagreement are the wide variety of carbon materials that are used as electrodes and because the kinetics of both the V(II)/V(III) and V(IV)/V(V) reactions on carbon depend on the electrode pretreatments. The role of surface functional groups and the mechanisms of electron transfer for these reactions is not well understood [1]. There is general agreement that the V(IV)/V(V) kinetics are more facile than the V(II)/V(III) kinetics [2, 3]. Multiple researcher groups have reported electrode overpotential increases with time, and “there is evidence that it occurs mainly on the negative electrode” [1]. Additionally, “reversing the polarity of the VRFB has been suggested as one strategy to recover lost performance but not all investigators have found this strategy effective” [1]. Exposing the V(II)/V(III) electrode to V(IV)/V(V) electrolyte may increase the roughness and oxidize the electrode, which can both improve the activity. It has also been suggested that reversing the polarity may remove impurities, such as copper metal from the negative electrode [4]. More recently, it has been proposed that surface activity may be improved by oxidizing adsorbed V(II) [5]. We hypothesize that V(II)/V(III) electrode degradation on graphitic carbon-fiber electrodes is primarily due to the adsorption of a contaminate that is oxidized when exposed to V(IV)/V(V) electrolyte. We will describe what we suspect is the relevant contaminate species, and we will show the stability of the V(II)/V(III) electrode can be substantially improved by simply removing certain electrolyte-wetted components from the VRFB test apparatus. References A. Bourke, D. N. Buckley, et.al., “JES, 170 (2020). 10.1149/1945-7111/acbc99 D. Aaron, T. A. Zawodzinski, et. al., ECS Electrochem. Letters, 2 (2013) 10.1149/2.001303eel N. Pour, Y. Shao-Horn, et.al., J. of Physical Chemistry C, 119 (2015).10.1021/jp5116806 D. Reynard, H. Girault, et.al., ChemSusChem, 12 (2019). 10.1002/cssc201802895T. Greese and G. Reichennauer, J. Power Sources, 500 (2021). 10.1016/j/jpowsour.2021.229958

A Stable Polymer-Blended Anion-Exchange Membrane for Enhanced Performance in Redox Flow Batteries

Redox flow batteries (RFBs) operate with a membrane, responsible for the separation of cationic active species and allowing the passage of counter-ions, to preserve electroneutrality on each side of RFBs. Commercial cation-exchange membranes (CEMs), such as Nafion®, possess excellent ionic conductivity and chemical stability. However, they face challenges in blocking cationic active species common in RFBs, leading to significant capacity loss over time. Anion-exchange membranes (AEMs) efficiently block active species with the assistance of the Donnan effect. Nevertheless, commercial AEMs lack acid stability and conductivity compared to their cationic counterparts.Polytetrafluoroethylene (PTFE)-reinforced quaternary ammonium cardo poly(ether)ketone (QPEK-C)-based membranes with Al2O3 additives (PQPAM), a heterogeneous AEM developed in our lab1, possess excellent ionic conductivity with low permeability of active species and good mechanical properties. PQPAM has demonstrated better acid stability than commercial AEMs. However, its acidic and oxidative stability require improvement, as evidenced by degradation after 250 hours of in-situ harsh RFB cycling due to the heterogeneous nature of PQPAM and the exposure of the susceptible QPEK-C-rich side to the electrolytes2. To address this issue, we propose a strategy to enhance the chemical stability of QPEK-C-based membranes by inhibiting the exposure of QPEK-C to oxidation agents through blending with a hydrophobic engineering thermoplastic like polybenzimidazole (PBI)3,4. Furthermore, PBI's known ability to protonate in acidic media will reinforce ionic conductivity and the separation of active species, thus improving the Donnan effect, in addition to enhancing chemical and mechanical stability.Elemental analyses and microscopy images confirm a homogeneous blending of PBI and QPEK-C, promising stability improvement. The results of ex-situ tests on ionic conductivity, cation permeability, and chemical stability align with the mentioned hypotheses, showcasing that blend of PBI/QPEK-C outperforms pure PBI and QPEK-C AEMs. Additionally, the mechanical properties of the PBI/QPEK-C blended AEMs are improved compared to pure QPEK-C AEMs and PBI/QPEK-C blended AEMs outperform pure PBI and QPEK-C AEMs in in-situ cycling tests with our patented titanium-cerium RFBs5. Moreover, this work will explore other strategies to improve the blended AEM properties, such as utilizing inorganic fillers or PTFE reinforcement.

Electrolyte Gradients and Capacity Drop in Large Flow Battery Tanks: From Experiments to Fluid-Dynamic Investigations

A study of the effects of electrolyte flow inside the tanks on electrical performance of an industrial-size Vanadium Redox Flow Battery (VRFB) is presented. The concentration of electrolytes feeding the stacks of VRFBs is crucial in determining the device voltage and overall power performance. Usually, the assumption of perfect mixing in the tanks is assumed, but the hydraulic behavior of large VRFB can deviate significantly from this assumption depending on the electrolyte flow rate, stochiometric factor and geometry of the tanks. In this study, the State of Charge (SoC) measurements have been analyzed, starting from the signal produced by an Open Circuit Voltage (OCV) cell. An experimental campaign has been conducted during charge/discharge roundtrip cycles at different current levels and constant stoichiometric factor. Building on the delay in the voltage response of the battery, a fluid-dynamic model was developed to study how the hydraulic behavior of electrolytes inside tanks influences the electrolyte concentration and, consequently, the SoC of the electrolyte that feeds the stack and the electrical time response of the battery. The model indicated that a stratification of charged electrolyte is responsible for this delay resulting in an initial voltage plateau. A different hydraulic behavior was found in each tank and in each charge/discharge phase. These results highlight the tank role in the industrial-scale VRFB performance. References Sanchez-Diez, E. Ventosa, M. Guarnieri, A. Trovò, C. Flox, R. Marcilla, F. Soavi, P. Mazur, E. Aranzabe, R. Ferret, “Redox flow batteries: status and perspective towards sustainable stationary energy storage”, J. Power Sources, 481, (2021) 228804.Kurilovich, A. Trovò, M. Pugach, K. J. Stevenson, M. Guarnieri. Prospect of Modeling Industrial Scale Flow Batteries – from Experimental Data to Accurate Overpotential Identification, Renew. Sust. Energ. Rev. 167, (2022) 112559.Trovò, V. Di Noto, J. E. Mengou, C. Gambaro, M. Guarnieri. Fast Response of kW-Class Vanadium Redox Flow Batteries, IEEE Trans. Sustain. Energy 12, (2021) 2413–2422.Trovò, M. Rugna, N. Poli, M. Guarnieri. Prospects for industrial vanadium flow batteries, Ceram. Int., 49 (14), (2023) 24487-24498.Maggiolo, A. Trovò, M. Guarnieri, “Reactant Flow in Flow Batteries”, in L. Cabeza (ed.), Encyclopedia of Energy Storage, vol. 4, pp. 231-242. Oxford: Elsevier. March 2022.A. Prieto-Díaz, S. E. Ibáñez, M. Vera. Fluid dynamics of mixing in the tanks of small vanadium redox flow batteries: Insights from order-of-magnitude estimates and transient two-dimensional simulations, Int. J. Heat Mass Transf. 216, (2023) 124567.Trovò, N. Poli, M. Guarnieri. New strategies for the evaluation of Vanadium Flow Batteries: testing prototypes, Cur. Opin. Chem. Eng. 37, (2022) 100853. Figure 1

Operando Visualization of Redox Flow Batteries Using Fluorescence Spectroscopy with Alizarin Red S Electrolyte

Redox flow batteries (RFBs) charge and discharge by transferring electrons between two pairs of redox species separated by a proton exchange membrane. Unlike traditional batteries that store energy in redox-active materials within an enclosed cell, RFBs store energy in liquid electrolytes housed in external reservoirs1. These electrolytes are pumped through the cell, enabling redox reactions on the surface of electrodes. The energy storage capacity of RFBs is determined by the concentration of the active species and the size of the reservoirs, making them a promising technology for large-scale energy storage applications2. While RFBs possess advantages such as long lifetime, flexible design for battery capacity and power, and rapid response, they suffer from drawbacks like low energy density, power density, and energy efficiency3. Efforts to address these issues have primarily focused on modifications to the electrode materials or the flow field4 , 5. However, evidence supporting performance enhancements often relies on global parameters such as energy efficiency, energy density, and voltage drop, lacking detailed mechanistic and microscopic studies. Real-time observation of the electrode-electrolyte interface during redox reactions and the transport of redox species in the flow field holds the potential to significantly contribute to understanding the electrode structure and mass transport phenomena in RFBs6. This understanding, in turn, facilitates prediction and purposeful enhancement of battery performance by developing desirable structures for both electrode and flow fields. Microscopy, particularly confocal microscopy, serves as a powerful tool for observing microscopic structures. Confocal microscopes yield sharper images with higher resolution than widefield microscopy, enabling rapid acquisition of high-resolution images.In this study, we employed a confocal laser scanning microscope for operando visualization of RFBs. We designed a transparent framework for the battery, allowing light to pass through, and covered its surface with a glass cover to visualize the porous carbon electrode. We selected a fluorescent redox-active species, Alizarin Red S to enable visualization using fluorescence spectroscopy. Leveraging its unique fluorescence properties, we established a correlation between fluorescence intensity and the state of charge. This innovative approach enables us to observe the distribution of electrolytes, the dynamics of redox reactions on the electrode surface (with fast speed of imaging ＜0.2s), the mass transfer behavior of the electrolyte on the electrode surface, and the uniformity of electrolyte flow in the flow field, including areas of stagnation or recirculation. Zhang, J. et al. An all-aqueous redox flow battery with unprecedented energy density. Energy Environ. Sci. 11, 2010–2015 (2018).Rubio-Garcia, J., Kucernak, A. & Charleson, A. Direct visualization of reactant transport in forced convection electrochemical cells and its application to redox flow batteries. Electrochem. commun. 93, 128–132 (2018).Tolmachev, Y. V. Flow Batteries From 1879 To 2022 And Beyond. Qeios 1–79 (2023).Wang, R. et al. Gradient-distributed NiCo2O4 nanorod electrode for redox flow batteries: Establishing the ordered reaction interface to meet the anisotropic mass transport. Appl. Catal. B Environ. 332, 122773 (2023).Kumar, S. & Jayanti, S. Effect of flow field on the performance of an all-vanadium redox flow battery. J. Power Sources 307, 782–787 (2016).Wong, A. A., Rubinstein, S. M. & Aziz, M. J. Direct visualization of electrochemical reactions and heterogeneous transport within porous electrodes in operando by fluorescence microscopy. Cell Reports Phys. Sci. 2, 100388 (2021).

(Invited) Operando Visualization of the Electrolyte Distribution in Vanadium Redox Flow Electrodes

Electrolyte transport losses are among the main factors that limit the performance of Vanadium Redox Flow Batteries (VRFBs)1. The electrolyte must percolate into the electrode and reach the reaction sites with minimum resistance to reduce such losses. The optimized electrolyte flow ensures that the reactants and products are transported to and away from the reaction sites freely and decreases the pumping losses of the electrochemical cell, increasing the overall efficiency of the battery system.The electrolyte distribution in a porous electrode is crucial for the stability and performance of the electrode. The presence of gas bubbles in the electrode reduces the electrochemically active surface, resulting in cell potential fluctuations. In addition, the gas bubbles cause poor contact between the electrolyte and the electrode, and the ionic conductivity could be locally blocked2. These effects lead to inhomogeneous potential distribution (spikes), accelerating the electrode material's corrosion. Gas bubbles are very common in VRFBs, and they result from parasitic side reactions, such as carbon corrosion, hydrogen evolution (HER), or incomplete electrode wetting3.Synchrotron X-ray imaging is a powerful tool for tracking these bubbles in porous carbon materials. We have designed an experimental setup resembling an operating VRFB cell to image the flow through the porous carbon electrode. With its modular structure, the setup offers excellent flexibility to evaluate different designs and operational aspects of VRFBs4, 5. The findings of our investigations over the years will be discussed in this presentation. References J. Kim and H. Park, Journal of Power Sources, 2022, 545, 231904. K. Krause, C. Lee, J. K. Lee, K. F. Fahy, H. W. Shafaque, P. J. Kim, P. Shrestha and A. Bazylak, ACS Sustainable Chemistry & Engineering, 2021, 9, 5570-5579. M.-A. Goulet, M. Skyllas-Kazacos and E. Kjeang, Carbon, 2016, 101, 390-398. L. Eifert, N. Bevilacqua, K. Köble, K. Fahy, L. Xiao, M. Li, K. Duan, A. Bazylak, P.-C. Sui and R. Zeis, ChemSusChem, 2020, 13, 3154-3165. K. Köble, L. Eifert, N. Bevilacqua, K. F. Fahy, A. Bazylak and R. Zeis, Journal of Power Sources, 2021, 492, 229660. Figure 1

Pegylated Viologen Derivatives to Improve Performance of Aqueous Organic Redox Flow Battery

Renewable energy sources like wind and solar power are great alternatives for a clean way to produce electricity but have the inconvenience to fluctuate1. To address this issue and promote the implementation of renewables sources, scientists are developing new ways to store energy while production is at a maximum for a subsequent release when there is demand. Redox flow batteries (RFBs) are the most appropriate solution and are increasingly gaining attention for stationary, large scale electrochemical energy storage2,3. One variation of RFBs are aqueous organic redox flow batteries (AORFBs), where water-soluble organic molecules are use as the redox couple. Viologen type molecules are particularly well-suited as a negative potential species to develop cheaper and better AORFBs with great scalability, reversibility and long-term stability4.In this study, viologen derivatives were synthesized with various N-functional groups to explore the impact of the substituent on their solubility, viscosity and redox potential. We showed that the use of short chains of poly(ethylene glycol) improved the solubility of the viologens derivatives which could lead to batteries with higher capacity. The symmetric viologen (with two identical substituents) provided a great solubility in water and the formal potential was unaffected by the chemical nature of the substituents. We demonstrated that the 1,1’-(bisethylene glycol)-4,4’-bipyridium (PEG2-V-PEG2) showed the most promising properties with a high solubility (2.3 M in 1M KCl) and low viscosity (3.01 mPa*s at 1M). As such, this derivative was selected for further evaluation in an asymmetrical labs-scale RFB prototype cell versus bis(trimethylamoniumpropyl)ferrocene (BTMAP-Fc). The compound was studied at various concentrations to assess the maximum energy density that can be reached and the effect of concentration on cycling life by achieving a comparison to the symmetrical 1,1’-bis(3-sulfonatopropyl)-4,4’-bipyridium (SPr-V-SPr) at 0.5 M. Figure 1: Redox flow battery scheme using Viologen derivative as the negolyte and BTMAP-Fc as the posolyte Reference Shi, X., Qian, Y. and Yang, S. Fluctuation analysis of a complementary wind–solar energy system and integration for large scale hydrogen production. ACS Sustainable Chemistry & Engineering, 8(18), pp.7097-7110. (2020)Sánchez-Díez, E.; Ventosa, E.; Guarnieri, M.; Trovò, A.; Flox, C.; Marcilla, R.; Soavi, F.;Mazur, P.; Aranzabe, E.; Ferret, R., Redox flow batteries: Status and perspective towards sustainable stationary energy storage. Journal of Power Sources, 481, 1-23. (2021)Poullikkas, A., A comparative overview of large-scale battery systems for electricity storage. Renewable and Sustainable energy reviews, 27, pp.778-788. (2013)Gentil, S., Reynard, D. and Girault, H.H. Aqueous organic and redox-mediated redox flow batteries: a review. Current Opinion in Electrochemistry, 21, pp.7-13. (2020) Figure 1

Synergetic Functionalization of the ZnS@ASCs Biocomposite: For Enhanced Electrochemical Performance of Redox Flow Batteries and Supercapacitors

Synergetic Functionalization of the ZnS@ASCs Biocomposite: For Enhanced Electrochemical Performance of Redox Flow Batteries and Supercapacitors

Evaluation of the effect of hydrogen evolution reaction on the performance of all-vanadium redox flow batteries

The exceptional advantages of vanadium redox flow batteries (VRFBs) have garnered significant attention, establishing them as the preferred choice for large-scale and long-term energy storage solutions. However, side reactions such as hydrogen evolution reaction (HER) lead to suboptimal performance of VRFB parameters, resulting in an overall decrease in VRFB performance. Therefore, it is imperative to investigate the mechanism by which HER affects VRFB performance and identify effective methods to mitigate its impact. In light of this, critical parameters such as charge-discharge curve, internal resistance, pressure-drop, pump power consumption, efficiency, and capacity retention rate are selected to evaluate the impact of HER on VRFB performance. Experimental results demonstrate that HER causes an increases in voltage during charging and a decrease during discharging stages leading to voltage loss; additionally, bubble generation significantly increases pressure drop and pump power consumption; furthermore, blockage of flow channels and electrodes due to bubbles leads to an increase in ohmic resistance. Finally, HER has a substantial impact on efficiency and capacity with an average energy efficiency of 2.92 %. After 60 cycles, the capacity retention rate decreased by nearly 7.69 %.

A high-performance aqueous Eu/Ce redox flow battery for large-scale energy storage application

We report the performance of an all-rare earth redox flow battery with Eu2+/Eu3+ as anolyte and Ce3+/Ce4+ as catholyte for the first time, which can be used for large-scale energy storage application. The cell reaction of Eu/Ce flow battery gives a standard voltage of 1.90 V, which is about 1.5 times that of the all-vanadium flow battery (1.26 V). Large standard voltage is conducive to the improvement of battery energy density and power density. The Eu2+/Eu3+electrode reaction in a NaCl solution on platinum electrode was investigated detailedly using cyclic voltammetry, linear sweep voltammetry, tafel plot and chronoamperometry. Unlike zinc-cerium flow battery, the active species of Eu/Ce flow battery are always present in the electrolyte, and no liquid-solid phase transition occurs. Thus, Eu/Ce flow battery is free of the problems associated with dendrite growth and theoretically have a longer cycle lifetime. The negative electrolyte is very sensitive to oxygen and can directly cause battery failure if exposed to air. The average energy efficiency of Eu/Ce flow battery exposed to air is only 22.0 %. However, the average energy efficiency of Eu/Ce flow battery stripped of oxygen reaches 82.7 % at 25 mA/cm2. Preliminary experimental studies have shown that Eu/Ce flow batteries are a promising method for large-scale energy storage.

Carbon nanofibers embedded in nanopores decorated graphite felt electrodes for enhanced vanadium redox flow batteries performance

This study introduces a novel electrode design, incorporating carbon nanofibers (CNFs) embedded in nanopores on graphite felt, achieved through a simplified one-step chemical vapor deposition process. The electrodes exhibit a uniform distribution of carbon nanofibers and nanopores, significantly enhancing active sites for vanadium redox reactions. Comprehensive characterization, including X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) surface area analysis, confirmed a significant increase in surface area and catalytic activity. When tested at a current density of 200 mA cm−2, the modified electrodes demonstrated a notable improvement in electrochemical performance, achieving over 75 % energy efficiency and maintaining this efficiency over 300 cycles. The cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS) results indicated enhanced kinetics and reduced charge transfer resistance. Post-mortem SEM images confirmed the structural integrity of the nanofibers after extensive cycling tests.

2-Acrylamido-2-methylpropane sulfonic acid (AMPS) grafted poly(vinylidene fluoride) (PVDF) membrane for improved vanadium redox flow battery (VRFB) performance

Polymer modification techniques are crucial for customizing material properties to suit specific applications, particularly in energy storage systems. This study investigates the modification of poly(vinylidene fluoride) (PVDF) membranes via atom transfer radical polymerization (ATRP) to graft 2-acrylamido-2-methylpropane sulfonic acid (AMPS) onto the fluorinated backbone. The successful grafting was confirmed via nuclear magnetic resonance (NMR) spectroscopy, while the membrane structure was evaluated using infrared (IR) and X-ray photoelectron spectroscopies (XPS). Thermogravimetric analysis (TGA) and universal testing machine (UTM) tests verified the thermal and mechanical stability of the membranes. Electrochemical analysis showed sustained performance over 300 cycles. The FluorCat-25 membrane demonstrated high coulombic efficiency (>98 %), voltage efficiency (83 %), and energy efficiency (81 %) at a current density of 100 mA cm−2. Notably, FluorCat-25 achieved a peak power density of 353 mW cm⁻², surpassing that of Nafion-117 (304 mW cm⁻²), with >85 % capacity retention, indicating its superior performance and suitability for VRFB applications. These findings position FluorCat-25 as a promising candidate for efficient and durable energy storage solutions in VRFB technology.

3-Dimensional numerical study on carbon based electrodes for vanadium redox flow battery

Electrode materials are critical in determining the performance of Vanadium redox flow batteries (VRFB). This work aims at elucidating the difference between carbon-based electrodes for VRFB. The electrodes considered for the present study are Graphite felt, Carbon felt, Carbon paper, and Carbon cloth. To study the characteristic behavior of different electrode materials, a 3D unit cell numerical model was developed by coupling electrolyte flow and electrochemical reactions and mass transfer module apart from considering the electrode structural and material information such as porosity, permeability, thickness, conductivity, and specific area. The simulation results of this study suggest that the Graphite felt is the optimum choice as an electrode material for VRFB as it offers higher electrocatalytic activity, lower pressure drop, better performance, and lower cost. The study is also extended to a multilayer configuration of Carbon Paper and Carbon Cloth. The performance of multi-layered electrodes by stacking single sheets of Carbon Paper and Carbon Cloth electrodes are matched to meet the performance obtained with the Graphite felt electrode. It has been shown with the help of polarization curve and the pressure drop study that the performance of five layers of carbon cloth and nine layers of carbon paper match the performance of Graphite felt, approximately. The present study provides practical guidance for the design and optimization of VRFB electrodes.

Aqueous Redox Flow Cells Utilizing Verdazyl Cations enabled by Polybenzimidazole Membranes.

Non-aqueous organic redox flow batteries (RFB) utilizing verdazyl radicals are increasingly explored as energy storage technology. Verdazyl cations in RFBs with acidic aqueous electrolytes, however, have not been investigated yet. To advance the application in aqueous RFBs it is crucial to examine the interaction with the utilized membranes. Herein, the interactions between the 1,3,5-triphenylverdazyl cation and commercial Nafion 211 and self-casted polybenzimidazole (PBI) membranes are systematically investigated to improve the performance in RFBs. The impact of polymer backbones is studied by using mPBI and OPBI as well as different pre-treatments with KOH and H3PO4. Nafion 211 shows substantial absorption of the 1,3,5-triphenylverdazylium cation resulting in loss of conductivity. In contrast, mPBI and OPBI are chemically stable against the verdazylium cation without noticeable absorption. Pre-treatment with KOH leads to a significant increase in ionic conductivity as well as low absorption and permeation of the verdazylium cation. Symmetrical RFB cell tests on lab-scale highlight the beneficial impact of PBI membranes in terms of capacity retention and I-V curves over Nafion 211. With only 2 % d-1 capacity fading 1,3,5-triphenylverdazyl cations in acidic electrolytes with low-cost PBI based membranes exhibit a higher cycling stability compared to state-of-the-art batteries using verdazyl derivatives in non-aqueous electrolytes.

Bioinspired flow Fields: A numerical investigation into Nature-Mimicking designs for boosting vanadium redox flow batteries

Efficient flow field structures are crucial for improving the performance of all-vanadium redox flow batteries (VRFBs). Considering the large pressure drop and pump losses in traditional serpentine flow fields (SFF), this paper proposes a novel biomimetic flow field structure (BFF) for VRFB. A three-dimensional multiphysics model comparing SFF and BFF designs for VRFB is developed, the assessment was further enhanced by considering the impact of electrolyte flow rates on multiple performance indicators. The results show that BFF’s unique design substantially reduces pressure drop, especially at higher flow rates. For both SFF and BFF designs, at a low flow rate of 60 ml/min, the SFF has a slightly higher pump-based voltage efficiency, but as the flow rate increases to 120 ml/min and 180 ml/min, the BFF outperforms the SFF, demonstrating advantages of 2.057 % and 6.888 %, respectively. This comprehensive VRFB modeling analysis provides valuable insights into optimizing future flow battery designs.

A gradient electrospinning electrode structure both in the in/through-plane directions for non-aqueous iron-vanadium redox flow battery

To boost the performance of non-aqueous redox flow batteries (RFBs), it is important to synergistically improve the flow/mass transfer efficiencies and the uniformity of overpotential distribution into the porous electrode. In this work, electrostatic spinning technology is developed to propose a novel porous electrode with gradient pore distribution both in the in-plane and through-plane directions, and applied in deep eutectic solvent (DES) electrolyte-based iron-vanadium RFB. On the one hand, the new in-plane gradient design modifies the distribution of reactive species of electrode near the membrane side, resulting in the decreasing polarization loss. On the other hand, the increasing porosity of electrodes from the flow field side to the membrane side attains a trade-off between the charge transfer and the electrolyte flow resistances. According to the experimental results, compared to the graphite felt electrode, the energy efficiency of this RFB with three-dimensional gradient electrode improves by 74.2 % at a current density of 10 mA·cm−2. Moreover, the numerical simulation reveals the reactive transfer behaviors of three-dimensional gradient porous electrode. The results show that the proposed three-dimensional gradient design can enhance the uniformity of overpotential distribution and achieve the decrease of polarization resistance, thus improving the performance of DES electrolyte-based iron-vanadium RFB effectively.

The Performance of All Iron-Based Redox Flow Batteries Enhanced by Carbon Nanotube Catalysts

The Performance of All Iron-Based Redox Flow Batteries Enhanced by Carbon Nanotube Catalysts