Performance Of Redox Flow Battery Research Articles

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.

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

Numerical simulation of all-vanadium redox flow battery performance optimization based on flow channel cross-sectional shape design

This paper numerically investigates optimizing trapezoidal flow channel cross-sectional shapes to improve all‑vanadium redox flow battery performance. A 3D steady-state multiphysics model coupling fluid dynamics, mass transfer, and electrochemistry was developed in COMSOL. Eight trapezoidal and one rectangular cross-section serpentine flow fields were simulated at varied flow rates. Results showed the TCS-T06 design reduced pressure drop by 12 % and pump power by 12 % versus the RCS. The concentration distribution of VO2+ was also improved, enhancing mass transfer. At 60 mA/cm2, TCS-T06 achieved 0.9 % higher pump power-based voltage efficiency. The optimized trapezoidal cross-section was proven to minimize losses, improve electrolyte distribution, and enhance VRFB performance. This work provides guidance for optimizing trapezoidal flow channel cross-sections to improve VRFB performance via enhanced mass transfer and reduced pressure drop.

Air Plasma Modification of Graphite-Based Electrode for Improved Performance of Aqueous Redox Flow Batteries

Graphite felt is widely utilized as a porous carbon electrode in aqueous redox flow batteries (RFBs). However, its inherent hydrophobic nature and limited electrochemical activity present challenges. While the correlation between RFB performance and electrode properties has been extensively studied for vanadium chemistry and other inorganic redox active materials, it remains scarce in literature for organic systems. In this study, we employ air plasma treatment, known for its controllability, solvent-free nature, and short treatment duration, to modify commercially available graphite felt for RFB applications. A comprehensive analysis is conducted to establish correlations between plasma treatment, physical properties, electrochemical characteristics, and overall cell performance in aqueous RFBs. Comparative evaluation reveals a significant enhancement, with treated graphite felt exhibiting an 85% increase in capacity at 140 mA cm−2 compared to its pristine counterpart. By intentionally utilizing authentic RFB electrodes and employing state-of-the-art ferrocyanide posolyte, this study underscores the crucial role of the interface, even for rapid (reversible) redox-active materials utilized in AORFBs.

Influence of Ni impurity ions in electrolyte on the performance of vanadium redox flow battery

Influence of Ni impurity ions in electrolyte on the performance of vanadium redox flow battery

Tungsten oxide embedded graphene oxide doped with SPEEK composite membrane for zinc–bromine redox flow batteries

Zinc-bromine redox flow batteries (Zn/Br2 RFBs) are fingerprint candidates for large-scale energy storage applications owing to their low cost, flexibility, high energy density, and astonishing round-trip efficiency. However, during the charging and discharging process, the diffusion of bromine through the porous membrane creates significant capacity decay and reduces the membrane efficiency of Zn/Br2 RFBs. In this respect, we developed various amounts of tungsten trioxide (WO3) nanoparticle-decorated graphene oxide (WO3@GO)-loaded sulfonated poly (ether ether ketone) (SPEEK) membranes and investigated their Zn/Br2 redox flow battery performance. The optimum amount of WO3@GO-loaded WO3@GO/SPEEK-3 membrane exhibits higher mechanical stability and ionic conductivity, significantly restricting the bromine crossover through the membrane. Due to their higher hydrophilic ability and uniform dispersion, WO3-loaded GO nanosheets provide strong interaction between the sulfonic acid group of the SPEEK membrane, which acts as an effective barrier for bromine crossover and significantly alters the Zn/Br2 battery performance. As a result, at a current density of 40 mA cm−2, the Zn/Br2 single cell of the WO3@GO/SPEEK-3 demonstrated higher coulombic efficiency (96.6 %), voltage efficiency (89.6 %), and energy efficiency (86.6 %), better than the WO3@GO/SPEEK-5 and pristine SPEEK membranes. These performances indicate that the proposed low-cost WO3@GO/SPEEK membrane can be highly applicable to other energy-related fields, including fuel cells and water treatment.

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.

Frequency and power shaving controller for grid-connected vanadium redox flow batteries for improved energy storage systems

In this research, the performance of vanadium redox flow batteries (VRFBs) in grid-connected energy storage systems centering on frequency and power sharing using voltage source inverters was evaluated. VRFBs are increasingly promising due to their scalability and long lifespan. We explore the impact of voltage source inverters on the frequency of the power supply when there is a change in load and power sharing between the grid and VRFB through MATLAB simulations. The test system demonstrates a storage system at an 11-kV substation and considers a load profile commencing from residential and commercial consumers. The outcome of this study reveals that VRFBs provide the required power to maintain load demand. Due to fast response time, VRFBs also regulate the frequency efficiently during the change in load demand and maintaining current total harmonic distortions (THDs). This research confirms the design and operation of VRFB-based energy storage systems, contributing to resilient grid infrastructure and reliable power distribution systems.

Implications of Polyoxometalate Properties on the Performance Characteristics of Redox Flow Battery

Implications of rate coefficients, concentration ratio, and electron-transfer number of the redox species present in the anolyte and catholyte on the performance characteristics of a redox flow battery (RFB) are investigated. Towards this, a polyoxometalate (POM)-V4+/V5+ RFB (with order 104 of magnitude difference in their rate coefficients) is assembled by replacing the anolyte (V2+/V3+) of a well-established vanadium RFB (VRFB); the redox potential of POM is comparable to that of V2+/V3+. The performance of the POM-V4+/V5+ RFB improves by ∼100 mV at reasonable operating current densities (∼ 200 mA cm−2) as compared to that of a VRFB, in a 5 cm2 cell, even though the solubility of tungstosilicic acid (TSA) is 300 mM as compared to 1.8 M VOSO4. Only four electrons can be reversibly extracted from the POM, although extraction of 14 electrons (theoretical) is possible from TSA, limiting the charging voltage to 1.4 V. Overcharging leads to capacity loss and concentration ratio (Catholyte: Anolyte) impacts the overall performance of RFB. Significant vanadium crossover loss is also observed at the anode side.

Measures of Performance of Vanadium and Other Redox Flow Batteries

The Vanadium redox flow battery and other redox flow batteries have been studied intensively in the last few decades. The focus in this research is on summarizing some of the leading key measures of the flow battery, including state of charge (SoC), efficiencies of operation, including Coulombic efficiency, energy efficiency, and voltage efficiency, and energy density. New formulas are presented to allow calculation of energy density, under varying circumstances, including varying ionic electrolyte concentrations, terminal voltage, discharge times and cycle numbers, and electron exchange numbers in the redox chemical reactions. Effects of ionic crossover and side reactions are addressed, and it is shown which forms of energy density are robust against these additional undesirable chemical reactions.

Binder-Free CNT-Modified Excellent Electrodes for All-Vanadium Redox Flow Batteries.

Electrodes are one of the key components that influence the performance of all-vanadium redox flow batteries (VRFBs). A porous graphite felt with modified fiber surfaces that can provide a high specific activation surface is preferred as the electrode of a VRFB. In this study, a simple binder-free approach is developed for preparing stable carbon nanotube modified graphite felt electrodes (CNT-GFs). Heat-treated graphite felt electrodes (H-GFs) are dip-coated using CNT homogeneous solution. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results conclude that CNT-GFs have less resistance, better reaction currents, and reversibility as compared to H-GF. Cell performances showed that CNT-GFs significantly improve the performance of a VRFB, especially for the CNT-GF served in the positive side of the VRFB. CNT presence increases the electrochemical properties of the graphite electrode; as a result, reaction kinetics for both VO2+/VO2+ and V3+/V2+ are improved. Positive CNT-GF (P-CNT-GF) configured VRFB exhibits voltage efficiency, coulombic efficiency, and energy efficiency of 85%, 97%, and 82%, respectively, at the operating current density of 100 mA cm-2. At high current density of 200 mA cm-2, the VRFB with P-CNT-GF shows 73%, 98%, and 72% of the voltage, coulombic, and energy efficiencies, respectively. The energy efficiency of the CNT-GF is 6% higher when compared with that of B-H-GF. The VRFB with CNT-GF can provide stable performance for 300 cycles at 200 mA cm-2.

Taurine-Functionalized Carbon Nanotubes as Electrode Catalysts for Improvement in the Performance of Vanadium Redox Flow Battery

The vanadium redox flow battery (VRFB) is a highly favorable tool for storing renewable energy, and the catalytic activity of electrode materials is crucial for its development. Taurine-functionalized carbon nanotubes (CNTs) were prepared with the aim of augmenting the redox process of vanadium ions and enhancing the efficiency of the VRFB. Sulfonated CNTs were synthesized through a simple modification process in a taurine solution and used as electrocatalysts for redox reactions involving VO2+/VO2+ and V2+/V3+. The SO3H-CNTs modified at 60 °C for 2 h exhibit the best electrocatalytic activity, showing higher redox peak current values compared to pristine carboxylated CNTs (COOH-CNTs). Sulfonic acid groups added to the surface of CNTs increase active sites for redox reactions and act as carriers for mass transfer and bridges for charge transfer, accelerating the rate of the electrode reactions. A battery consisting of SO3H-CNTs as catalysts demonstrates the outstanding charge–discharge performance at a current density of 300 mA∙cm−2. This configuration displays voltage and energy efficiencies of 81.46% and 78.83%, respectively, representing enhancements of 6.15% and 6.12% compared to that equipped with conventional graphite felts (75.31%, 72.71%). This study illustrates that taurine-functionalized carbon nanotubes serve as an efficient and promising catalyst for both the anode and cathode, leading to the improved performance of the VRFB.

Morphological Properties and Electrochemical Performance for Compressed Carbon-fiber Electrodes in Redox Flow Batteries

Abstract Improving reactor performance of redox flow batteries is critical to reduce capital cost, and one of the main contributions to the internal resistance is generated by the electrodes, which also impact the pressure drop of the stack. Porous electrodes with optimized microstructure and physiochemical properties play a key role in enhancing electrochemical and fluid dynamic performance. Electrode compression significantly impacts morphology and battery behavior, but the relationship between microstructure and performance remains unclear. In the present study, three representative, commercially available, carbon-fiber electrodes (i.e., paper, felt, and cloth) with distinct microstructures were investigated, and a comprehensive study was conducted to compare morphology, hydraulic permeability, mechanical behavior, electrochemical performance in a lab-scale vanadium redox flow battery at compression ratios of 0-50%. The 3D electrode morphology was characterized through X-ray computed tomography and the extracted microstructure parameters (e.g., surface area and tortuosity) were compared with corresponding electrochemically determined parameters. The optimal trade-off between fluid dynamics and electrochemical performance occurred at the compression ratios of 30%, 20%, and 20% for the felt, paper, and cloth, respectively. Owing to the bi-modal porosity of the woven microstructure, the cloth showed a better trade-off between the electrochemical performance and pressure drop than the other electrodes.

Hydrated eutectic electrolyte as catholyte enables high-performance redox flow batteries

Compared with conventional electrolytes, eutectic electrolytes are recognized as an ideal electrolyte for the next-generation electrochemical energy storage system characterized by facile synthesis and composition tunability. However, the eutectic electrolytes still suffer from sluggish kinetics, which inhibit their widespread application in redox flow batteries. Here, a well-designed hydrated eutectic electrolyte system (HEE) composed of iron chloride hexahydrate, urea and water with stoichiometric ratio at 2:1:6 is developed as catholyte to improve the cycling performance of hybrid redox flow batteries. The HEEs with precisely controlled water content could inhibit the water-induced side reactions, while expand the electrochemical stability windows. Moreover, the water molecules gradually replace the anions to participate in the solvation sheath of Fe3+ ions, forming a solvation structure of [FeClx(H2O)y]3−x, which result in an improved ion dissociation degree, ionic conductivity and redox kinetics. As a result, hybrid iron-based redox flow battery based on the optimal HEE exhibits a highly reversibly redox reaction of Fe3+/Fe2+ and reduced overpotentials. Furthermore, the battery could stably cycle over 120 cycles with a capacity retention of 87.75 % at a relatively high current density of 10 mA cm−2, delivering a maximum power density of ∼50 mW cm−2, which is much higher than reported eutectic-based flow batteries. This research offers new insights into rationally designing of advanced eutectic electrolytes for high-efficient redox flow batteries.

Development of Aqueous Organic Flow Battery Using SPEEK Membrane and Eco-Friendly Electrolytes

Aqueous organic redox flow batteries (AORFBs) are a type of flow battery that offers a promising solution for energy storage, and one of the main issues is selecting low-cost membranes with high ion conductivity to enhance performance and efficiency. In this study, low-cost sulfonated poly ether ether ketone (SPEEK) membranes were fabricated using the casting method, with the polymer/solvent ratios of SPEEK and N,N'-dimethylformamide (DMF) being varied. The Nafion 117 membrane was used as a benchmark for comparison. The performance of aqueous organic redox flow batteries employing anthraquinone-2-sulfonic acid (AQS) and 1,2-benzoquinone-3,5-disulfonic acid (BQDS) as electrolytes was evaluated. The SPEEK membranes were determined to have dense, homogeneous surfaces with no flaws and a thickness of 60 microns. In addition, their physicochemical properties, such as water uptake, swelling ratio, ion exchange capacity, and degree of sulfonation, were investigated. The results showed that the SPEEK membranes had better rate performance and cycle stability when compared to the Nafion117 membrane during charge-discharge cycles. Additionally, the SPEEK membranes exhibited slower potential drops and higher power density during constant current mode operation, despite showing no significant differences in energy efficiency and power density. These findings demonstrate the potential of SPEEK membranes for use in AORFBs and as a benchmark for future research and development.

Substituent Impact on Quinoxaline Performance and Degradation in Redox Flow Batteries.

Aqueous redox flow batteries (RFBs) are attractive candidates for low-cost, grid-scale storage of energy from renewable sources. Quinoxaline derivatives represent a promising but underexplored class of charge-storing materials on account of poor chemical stability in prior studies (with capacity fade rates >20%/day). Here, we establish that 2,3-dimethylquinoxaline-6-carboxylic acid (DMeQUIC) is vulnerable to tautomerization in its reduced form under alkaline conditions. We obtain kinetic rate constants for tautomerization by applying Bayesian inference to ultraviolet-visible spectroscopic data from operating flow cells and show that these rate constants quantitatively account for capacity fade measured in cycled cells. We use density functional theory (DFT) modeling to identify structural and chemical predictors of tautomerization resistance and demonstrate that they qualitatively explain stability trends for several commercially available and synthesized derivatives. Among these, quinoxaline-2-carboxylic acid shows a dramatic increase in stability over DMeQUIC and does not exhibit capacity fade in mixed symmetric cell cycling. The molecular design principles identified in this work set the stage for further development of quinoxalines in practical, aqueous organic RFBs.

Surface Electroactive Sites of Tungstated Zirconia Catalysts for Vanadium Redox Flow Batteries.

Surface electroactive sites for tungstate zirconia (WZ) were created by utilizing tungstate-immobilized UiO-66 as precursors via a double-solvent impregnation method under a mild calcination temperature. The WZ-22-650 catalyst, containing a moderate W content (22%), demonstrated a high density of surface electroactive sites. Proper heat treatment facilitated the binding of oligomeric tungsten clusters to stabilized tetragonal ZrO2, resulting in improved catalytic performance toward the VO2+/VO2+ redox couples compared to other tested samples. The substantial surface area, mesoporous structure, and establishment of new W-O-Zr bonds affirm the firm anchoring of WOx to ZrO2. This robust attachment enhances surface electroactive sites, elevating the electrochemical performance of vanadium redox flow batteries (VRFBs). Charge-discharge tests further demonstrate that the superior voltage efficiency (VE) and energy efficiency (EE) for VRFBs using the WZ-22-650 catalyst are 87.76 and 83.94% at 80 mA cm-2, which are 13.42% VE and 10.88% EE better than heat-treated graphite felt, respectively. Even at a higher current density of 160 mA cm-2, VRFBs utilizing the WZ-22-650 catalyst maintained considerable efficiency, recording VE and EE values of 76.76 and 74.86%, respectively. This facile synthesis method resulted in WZ catalysts displaying superior catalytic activity and excellent cyclability, offering a promising avenue for the development of metal-oxide-based catalysts.

Multiple‐dimensioned defect engineering for graphite felt electrode of vanadium redox flow battery

AbstractThe scarcity of wettability, insufficient active sites, and low surface area of graphite felt (GF) have long been suppressing the performance of vanadium redox flow batteries (VRFBs). Herein, an ultra‐homogeneous multiple‐dimensioned defect, including nano‐scale etching and atomic‐scale N, O co‐doping, was used to modify GF by the molten salt system. NH4Cl and KClO3 were added simultaneously to the system to obtain porous N/O co‐doped electrode (GF/ON), where KClO3 was used to ultra‐homogeneously etch, and O‐functionalize electrode, and NH4Cl was used as N dopant, respectively. GF/ON presents better electrochemical catalysis for VO2+/VO2+ and V3+/V2+ reactions than only O‐functionalized electrodes (GF/O) and GF. The enhanced electrochemical properties are attributed to an increase in active sites, surface area, and wettability, as well as the synergistic effect of N and O, which is also supported by the density functional theory calculations. Further, the cell using GF/ON shows higher discharge capacity, energy efficiency, and stability for cycling performance than the pristine cell at 140 mA cm−2 for 200 cycles. Moreover, the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm−2. Such an ultra‐homogeneous etching with N and O co‐doping through “boiling” molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.

Improving the electrochemical characteristics and performance of a neutral all-iron flow battery by using the iron reduction bacteria

At present, the all-iron redox flow batteries (RFBs) have greater application potential due to high accessibility of electrolytes compared to traditional RFBs. Meanwhile, although electroactive bacteria can accelerate the electrons transfer, their potential to improve the performance of RFBs has been overlooked. Previously, we had confirmed that ferrous-oxidizing bacteria (FeOB) could enhance the performance of an all-iron RFB, therefore we conducted several batch experiments and chronopotentiometry experiments by using the ferric-reducing bacteria (FeRB) or mixed culture (FeOB and FeRB) to demonstrate whether they have the same or stronger effects on Fe3+-DTPA/Na4[Fe(CN)6] RFB. The results showed that the experimental reactors could achieve higher charging current density and initial cathodic potential during constant voltage charging process. The electrochemical impedance spectroscopy data and cyclic voltammetry curves demonstrated that the polarization impedance increased slower and reduction peak potential of experimental groups also emerged a positive shift compared to CK. According to chronopotentiometry experiments results, the microbes could function at maximum 0.3 M, 12 mA/cm2, and also improved the charging specific capacity. Combined the SEM pictures and microbial composition analysis, the main functional electroactive FeRB were Alcaligenes, Corynebacterium and Bacillus, which indicated to have important potential in improving the performance of RFBs.

Maneuverable B-site cation in perovskite tuning anode reaction kinetics in vanadium redox flow batteries

The actual performance of vanadium redox flow batteries (VRFBs) is still significantly constrained by the slow kinetics and major parasitic reactivity of anode issues. Herein, a B-site management strategy of SrBO3 (B = Ti, Zr, Hf) perovskites was proposed to promote the anode reaction jointly explored by experiments and first–principle calculations. As the atomic number of B increases, the enhanced polarity of the B–O bond and the increased oxygen defect can boost the adsorption of vanadium ions, while the weakened orbital hybridization of the B–O bond facilitates the charge transfer of anode reaction. Compared with SrTiO3 and SrZrO3, oversized particles and deformed crystals of SrHfO3 reduce its catalysis. Of SrBO3 perovskites, SrZrO3 stands out in catalysis, owing to its outstanding combination of high hydrophilicity, large surface area, and desired crystal structure. Further, the VRFB using SrZrO3 presents a superior energy efficiency (EE) of 63.2% at 300 mA cm–2 and an increase of 15% in EE compared with the pristine cell at 200 mA cm–2. This work lays the foundation for building the connections between the structural and compositional flexibility and the tunable perovskite properties desirable for vanadium redox reactions.