Flow Battery Research Articles

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N, N, N-trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s−1) as well as high water-solubility (∼2.6 M in H2O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ3+) formed via the disproportionation of radical di-cations (NEt-POZ2+) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

Correlation Between Microscopic Current Fluctuations Observed at Ultra-Microelectrodes and Macroscopic Bulk Electrolysis Performance in Redox-Active Microemulsions

Abstract Microemulsions (µEs) have been proposed as redox flow battery (RFB) electrolytes that maximize ionic conductivity and charge capacity by synergizing two immiscible phases. However, charge transfer during electrolysis in µEs is poorly understood. Here, we show that ultramicroelectrode electrolysis of ferrocene-loaded µEs - 20%, 60%, and 90% water - reveals stochastic current fluctuations. These are differentiated in the scanning electrochemical microscopy (SECM) geometry, where power spectral density analysis showed distinct changes in the frequency contributions. SECM in the substrate generation-tip collection mode showed that fluctuations arise under mass-transfer control. Significant differences in the diffusion coefficient of ferrocene species were deducted from SECM approach curves, suggesting phase transfer behavior. Using bulk electrolysis, we calculated the charge accessibility and cycling behavior in the µEs. A decrease in the stochastic behavior of the µEs seems to correlate to a higher accessibility and cycling performance, with the 90% water µE displaying the best reversibility and the 60% the lowest. Altogether, these results suggest that Marangoni-type convection driven by concentration gradients and/or µE restructuring during charge transfer play a role in the electrochemical performance of µEs. This presents opportunities for screening and diagnosing the performance of these emerging RFB electrolytes.

Enhancing Vanadium Redox Flow Battery Performance with ZIF-67-Derived Cobalt-Based Electrode Materials

Vanadium redox flow batteries (VRFBs) have emerged as a promising energy storage solution for stabilizing power grids integrated with renewable energy sources. In this study, we synthesized and evaluated a series of zeolitic imidazolate framework-67 (ZIF-67) derivatives as electrode materials for VRFBs, aiming to enhance electrochemical performance. Four materials—Co/NC-700, Co/NC-800, Co3O4-350, and Co3O4-450—were prepared through thermal decomposition under different conditions and coated onto graphite felt (GF) electrodes. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses confirmed the structural integrity and distribution of the active materials. Electrochemical evaluations revealed that electrodes with ZIF-67-derived coatings exhibited significantly lower charge transfer resistance (Rct) and higher energy efficiency (EE) compared to uncoated GF electrodes. Co/NC-800//GF delivered the highest energy efficiency and discharge capacity among the tested configurations, maintaining stable performance over 100 charge–discharge cycles. These results indicate that Co/NC-800 holds great potential for use in VRFBs due to its superior electrochemical activity, stability, and scalability.

System-Level Dynamic Model of Redox Flow Batteries (RFBs) for Energy Losses Analysis

This paper presents a zero-dimensional dynamic model of redox flow batteries (RFBs) for the system-level analysis of energy loss. The model is used to simulate multi-cell systems considering the effect of design and operational parameters on energy loss and overall performance. The effect and contribution of stack losses (e.g., overpotential and crossover losses) and system losses (e.g., shunt currents and pumps) to total energy loss are examined. The model is tested by using literature data from a vanadium RFB energy storage. The results show that four parameters mainly affect RFB system performance: manifold diameter, stack current, cell standard potential, and internal resistance. A reduction in manifold diameter from 60 mm to 20 mm reduced shunt current loss by a factor of four without significantly increasing pumping loss, thus boosting round-trip efficiency (RTE) by 10%. The increase in stack current at a low flow rate increases power, while the cell standard potential and internal resistance play a crucial role in influencing both power and energy output. In summary, the modeling activities enabled the understanding of critical aspects of RFB systems, thereby serving as tools for system design and operation awareness.

Unlocking Molecular Interactions of Biredox Eutectic Electrolyte for Non‐Aqueous Symmetrical Organic Redox Flow Batteries

AbstractBiredox deep‐eutectic solvents (DESs)‐based electrolytes have shown unique features in non‐aqueous asymmetrical redox flow batteries (RFBs) that can potentially mitigate the crossover issue. However, strong intermolecular interactions among the electrolyte constituents in DESs bring in practical challenges such as limited mass transfer rates, slow redox kinetics, and degraded cyclability. Here, by using a novel biredox‐type DES based on 4‐methoxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (4‐MeO‐TEMPO) and 3,3′‐dimethylazobenzene (3,3′‐Azo) as a model electrolyte system, the intermolecular interaction involving in the biredox DESs is unlocked by first‐principles calculations, and their influence on the electrochemical performance of biredox DESs couples is systematically investigated in comprehensive consideration of the solvents and the supporting salts. It demonstrates that employing tetrabutylammonium bis‐trifluoromethane sulfonimidate‐acetonitrile as the supporting electrolyte synergistically weakens the intermolecular interactions within the DESs, thereby significantly promoting the redox kinetics and electrochemical reversibility in non‐aqueous symmetrical RBFs. With such an optimized electrolyte, a prototype symmetrical cell under static mode is capable of delivering a high output voltage of ∼2.15 V, a decent cyclability, and the exceptional rate capability with a current density of 25 mA cm−2. This study provides a simple yet effective way to develop advanced RFBs with dependable electrolyte regulation.

Zinc‐Ferricyanide Flow Batteries Operating Stably under −10 °C

AbstractAlkaline ferri/ferro‐cyanide‐based flow batteries are well suited for energy storage because of their features of high electrochemical activity, good kinetics and low material cost. However, they suffer from low energy density and poor temperature adaptability. The ferri/ferro‐cyanide catholyte exhibits low solubility (~0.4 M at 25 °C) in NaOH‐ or KOH‐based supporting electrolyte and can easily form precipitates below room temperature. Here we report a lithium‐based supporting electrolyte that significantly enhances the solubility of ferrocyanide. The use of LiOH intensifies the ion‐dipole interaction between water molecules and solutes and cripples polarization among ferrocyanide ions. Thus, we have achieved a ferrocyanide‐based catholyte of 1.7 M at 25 °C and of 0.8 M at −10 °C. A zinc‐ferricyanide flow battery based on the lithium‐based supporting electrolyte demonstrates a steady charge energy of ~72 Wh L−1catholyte at 25 °C, and maintains stable for ~4200 cycles (~4200 hours). Furthermore, it remains stable for ~800 cycles (~800 hours) at −10 °C.

Nanocellulose-based ion-selective membranes for an aqueous organic redox flow battery

Nanocellulose-based ion-selective membranes for an aqueous organic redox flow battery

Regulating Molecular Interactions in Polybenzimidazole Membrane for Efficient Vanadium Redox Flow Battery.

The tightly bonded structure of polybenzimidazole (PBI) membrane is the origin of its poor proton conductivity, which severely hinders achieving a cost-effective membrane for vanadium redox flow battery (VRFB). It desires a strategy to relax the membrane structure to significantly improve the proton conductivity and maintain its structure stability. Therefore, this work proposes a novel strategy through regulating molecular interactions within PBI membrane to loosen up the structure of PBI membrane and dramatically enhance the proton conductivity. The interactions in PBI membrane are switched by DMSO/water and acid through sequentially treating membrane with these solutions. The efficient PBI membrane prepared using this strategy demonstrates an outstanding performance for VRFB, with the proton conductivity enhanced by 3850% (from 1.9 to 76.3 mS cm-1), and VRFB achieves a high energy efficiency of 80.5% under 200 mA cm-2. More importantly, this work shed lights on the structure-property relationship of PBI membrane, and the mechanism in enhancing proton conductivity is unraveled, which is of great significance for the development of VRFB membranes.

Soft-hard zwitterionic additives for aqueous halide flow batteries.

Aqueous redox flow batteries with halide-based catholytes (where the halogen atom (X) is Br or I) are promising for sustainable grid energy storage. However, the formation of polyhalides during electrochemical charging and the associated phase separation into X2 limits the operable state of charge (SoC), results in vaporization and self-discharge inefficiencies, and spurs complete device failure1-3. Here we introduce soft-hard zwitterionic trappers (SH-ZITs) as complexing agents composed of a polyhalide-complexing 'soft' cationic motif and a water-soluble 'hard' anionic motif to enable homogeneous halide cycling. More than 300 structures were designed and 13 were characterized, showcasing the ability to complex polyhalides in homogeneous aqueous solution, to deter cation-exchange membrane crossover and to alter the electrochemical electrode mechanism. In flow battery cycling at a standard catholyte SoC of 66.6 per cent (stoichiometrically X3-), an average coulombic efficiency of more than 99.9 per cent at 40 milliamperes per square centimetre with no apparent decay was observed after more than 1,000 cycles over 2 months, with stability at elevated temperatures also demonstrated. Interestingly, SH-ZITs enable homogeneous cycling of the halide catholyte up to 90 per cent SoC at 2 moles per litre (47.7 ampere-hours per litre) for bromide, revealing previously unknown polyhalide regimes to be studied. Ultimately, SH-ZIT enables ultrahigh catholyte capacity utilization up to over 120 ampere-hours per litre at 80 per cent SoC with homogeneous cycling as well as the ability to pair with a zinc anode in a hybrid flow battery.

Promises and challenges of polyoxometalates (POMs) as an alternative to conventional electrolytes in redox flow batteries (RFBs)

Promises and challenges of polyoxometalates (POMs) as an alternative to conventional electrolytes in redox flow batteries (RFBs)

New Redox Chemistries of Halogens in Aqueous Batteries.

Halogen-based redox-active materials represent an important class of materials in aqueous electrochemistry. The existence of versatile halogen species and their rich bonding coordination create great flexibility in designing new redox couples. Novel redox reaction mechanisms and electrochemical reversibility can be unlocked in specifically configurated electrolyte environments and electrodes. In this review, the halogen-based redox couples and their appealing redox chemistries in aqueous batteries, including redox flow batteries and traditional static batteries, that have been studied in recent years are discussed. New aqueous electrochemistry provides hope to outperform the state-of-the-art materials and systems that are facing resources and performance limitation, and to enrich the existing battery chemistries.

Metal Coordination Compounds for Organic Redox Flow Batteries

AbstractAlong with the continuous optimization of the energy structure, more and more electricity come from intermittent renewable energy sources such as wind and solar energy. Redox flow batteries (RFBs) have the advantage that energy and power can be regulated independently, so they are widely used in large‐scale energy storage. Redox active materials are the important components of RFBs, which determine the performance of the battery and the cost of energy storage. Some metal coordination compounds (MCCs) and their derivatives have been considered redox active materials that can replace metal‐based redox flow batteries due to their properties such as tunability, high abundance and sustainability. MCCs can provide higher energy density because they are highly soluble both in the initial state and in any charged state during the battery cycling process. MCCs have also attracted a lot of attention from researchers because of their high economic value, low toxicity, and wide availability. This review provides an overview of the recent development of soluble metal coordination compounds, such as Ferrocene, and concludes with an in‐depth discussion of the prospects of metal coordination compounds for application in organic redox flow batteries.

Sensitivity of Capacity Fade in Vanadium Redox Flow Battery to Electrolyte Impurity Content.

The gradual capacity decrease of vanadium redox flow battery (VRFB) over long-term charge-discharge cycling is determined by electrolyte degradation. While it was initially believed that this degradation was solely caused by crossover, recent research suggests that oxidative imbalance induced by hydrogen evolution reaction (HER) also plays a significant role. In this work by using vanadium pentoxides with different impurities content, we prepared three grades of vanadium electrolyte. By measuring electrochemical properties on carbon felt electrode in three-electrode cell and VRFB membrane-electrode assembly we evaluate the influence of impurity content on battery polarization and rate of side reactions which is indicated by the increase of average oxidation state (AOS) during charge-discharge tests and varies from 0.061 to 0.027 day-1 for electrolytes made from 99.1 and 99.9 wt % V2O5. We found that increase of AOS correlates with the increase of open-circuit voltage of VRFB in the discharged state ranging from 9.6 to 14.9 mV day-1 for highest and lowest electrolyte purity levels, respectively. While AOS increase is significant, it does not solely determine capacity fade. It is demonstrated that the presence of vanadium crossover decreases capacity fade, i. e. levels the contribution of side reactions on capacity drop.

Homogeneous Complexation Strategy to Manage Bromine for High‐Capacity Zinc–Bromine Flow Battery

AbstractZinc–bromine flow batteries (ZBFBs) have received widespread attention as a transformative energy storage technology with a high theoretical energy density (430 Wh kg−1). However, its efficiency and stability have been long threatened as the positive active species of polybromide anions (Br2n+1−) are subject to severe crossover across the membrane at a high concentration. Herein, a novel highly hydrophilic complexing agent, N‐methyl‐N, N‐bis(2‐hydroxyethyl)‐1‐propanaminium bromide (PMDA), is developed to effectively manage bromine in a homogeneous posolyte, which realizes a low bromine crossover at a high operating concentration in ZBFBs. Both theoretical and experimental results suggest that the PMDA interacts with Br2n+1− and forms a larger‐size complex PMDABr2n+1. When adding 0.40 m PMDA, the bromine stays homogeneous at a high concentration up to 1.20 m, and its permeability is remarkably decreased by 74%. For demonstration, the ZBFB achieves a operating capacity record of 57.2 Ah L−1 in a homogeneous bromine posolyte with a high Coulombic efficiency of ≈90.0% and superior cycling stability (capacity retention rate of 100.0% per cycle). This work provides one innovative bromine management strategy to realize a high capacity and superior stability in ZBFBs.

In Situ Molecular Reconfiguration of Pyrene Redox-Active Molecules for High-Performance Aqueous Organic Flow Batteries.

Aqueous organic flow batteries (AOFBs) hold great potential for large-scale energy storage, however, scalable, green, and economical synthetic methods for stable organic redox-active molecules (ORAMs) are still required for their practical applications. Herein, pyrene-based ORAMs are obtained via an in situ organic electrolysis strategy in a flow cell. It is revealed that the water attacking pyrenes restructured molecules to produce a variety of isomers and dimers during the electrolysis, which can be modulated by regulating the local electron cloud density and steric hindrance of pyrene precursors. As a result, the molecularly reconfigured pyrene-based catholytes, even without any further purification, achieved a high electrolyte utilization of ≈96% and volumetric capacity above 50AhL-1. Inspiringly, remarkable cell stability with almost no capacity decay for ≈70 days is achieved, benefiting from the robust aromatic structure of the pyrene cores. The insights into the in situ electrosynthesis of pyrene-based ORAMs provided in the work will provide guidance for designing ultra-stable ORAMs for AOFB applications.

Strategically Modified Ligand Incorporating Mixed Phosphonate and Carboxylate Groups to Enhance Performance in All‐Iron Redox Flow Batteries

AbstractIron redox flow batteries (Fe‐RFBs) hold significant promise for achieving cost‐effectiveness and utilizing abundant materials for stationary energy storage applications. Here, a design of a novel Fe complex utilizing a nitrogenous phosphonate/carboxylate mixed ligand, N,N‐Bis(phosphonomethyl)glycine (BMPG), is presented to achieve high performance Fe anolyte. Compared to its all‐phosphonate form, nitrilotri(methylphosphonic acid) (NTMPA), the new complex Fe(BPMG)2 demonstrates a negatively shifted redox potential, resulting in ≈0.07 V (≈10%) increase in battery output voltage. Full battery testing paired with ferrocyanide catholyte demonstrates stable cycling (capacity degradation <0.0001%/cycle) over 730 consecutive charge/discharge cycles with Coulombic Efficiency of 100% at a current density of 20 mA cm−2 under near neutral pH (≈8). Of particular interest, density functional theory (DFT) studies and operando Raman measurements provide strong evidence supporting a molecular structure in BPMG, which reveals the mixed phosphonate/carboxylate groups in BPMG maintain the octahedral coordination of the Fe ion center with phosphonates exclusively, while leaving the carboxylate unbound for both Fe(II) and Fe(III) complexes. This structural similarity between BPMG‐based Fe(II) and Fe(III) complexes effectively mitigates the slow redox reaction kinetics observed in Fe(NTMPA)2 anolyte, where significant ligand reorientation occurs between Fe(II) and Fe(III) complexes.

Key Issues of Salt Cavern Flow Battery

Salt cavern flow batteries (SCFBs) are an energy storage technology that utilize salt caverns to store electrolytes of flow batteries with a saturated NaCl solution as the supporting electrolyte. However, the geological characteristics of salt caverns differ significantly from above-ground storage tanks, leading to complex issues in storing electrolytes within salt caverns. Therefore, investigating and summarizing these issues is crucial for the advancement of SCFB technology. This paper’s innovation lies in its comprehensive review of the current state and development trends in SCFBs both domestically and internationally. First, the current development status of SCFB energy storage technology both domestically and internationally is summarized. Then, eight main issues are proposed from the perspectives of salt cavern geological characteristics (tightness, conductivity, ions, and temperature) and electrolyte properties (selection, permeability, corrosion, and concentration). Finally, a novel SCFB system is proposed to address the most critical issue, which is the low concentration and uneven distribution of active materials in the current SCFB system. The review in this paper not only comprehensively summarizes the development status of SCFBs both domestically and internationally, but also points out the direction for the future research focussing on SCFBs.

Advanced Poly(vinyl chloride)-Based Membranes Functionalized with Amino Compounds for Vanadium Redox Flow Batteries

Advanced Poly(vinyl chloride)-Based Membranes Functionalized with Amino Compounds for Vanadium Redox Flow Batteries

Acetylacetonate-modified TiO2 nanoparticles coated on the carbon felt as the negative electrode of vanadium redox flow battery for reducing HER and enhancing V3+/V2+ redox reactions

The occurrence of the hydrogen evolution reaction (HER) on the surface of the carbon-based negative electrode of the vanadium redox flow battery (VRFB) causes high charge transfer resistance (RCT) for the desired V3+/V2+ redox reaction leading to irreversible capacity loss. To this effect, we have synthesized acetylacetonate-modified TiO2 (SGTA) and unmodified TiO2 (SGT) coating colloidal solutions as electrocatalysts for enhanced V3+/V2+ redox reaction on the carbon-felt negative electrodes of VRFB. The SGTA particles exhibit significantly higher homogeneity with sizes of ≤15 nm, in comparison to the severely aggregated SGT particles with diameters of ∼23–75 nm in colloidal solution. When coated on the pristine carbon felt (P-CF), the surface morphology of the SGTA@CF electrode exhibits relatively dense, uniformly coated particles, in comparison to the sparse, non-even coating of aggregated particles on the SGT@CF electrode surface. Consequently, the charge transfer for V3+ → V2+ reduction reaction and charge storage capacity are determined to be in the order SGTA@CF > SGT@CF > P-CF, confirming that the competitive and irreversible HER was higher on the surface of non-evenly coated fibers and bare carbon felt, respectively.

The Effect of Electrochemical Ageing of Glassy Carbon Electrodes on VII-VIII and VIV-VV Kinetics

Abstract Electrode activity towards the negative and positive half-cell reactions of a vanadium flow battery were investigated. Cyclic voltammetry and electrochemical impedance spectroscopy were employed to monitor electrode activity of glassy carbon electrodes towards VII-VIII and VIV-VV redox reactions during electrochemical ageing through repeated anodic and cathodic treatments.
Electrode activity is found to increase with number of treatment steps, showing little difference initially between anodised and cathodised electrodes. However, after several treatments, a potential-differentiated behaviour emerges, with distinct enhanced and inhibited states. For VII-VIII, anodised electrodes showed enhanced activity, while cathodised electrodes were inhibited. Conversely, for VIV-VV, cathodised electrodes had enhanced activity. In almost all cases, the activity is greater than that of an untreated electrode.
Eventually, electrode activities stabilise in a steady-state region where activity depends on the final treatment potential rather than the number of steps. In this region, activity can be toggled reproducibly between enhanced and inhibited states. Therefore, it can be concluded that functional groups, rather than surface roughening or defect formation, are responsible for this toggling capability. Furthermore, for VIV-VV, number of treatment steps required to reach and the activity levels in this region are found to be dependent on the upper and lower treatment potentials.