Flow Battery Research Articles

Chitosan Composite Membrane with Efficient Hydroxide Ion Transport via Nano-Confined Hydrogen Bonding Network for Alkaline Zinc-Based Flow Batteries.

The development of membranes with rapid and selective ionic transport is imperative for diverse electrochemical energy conversion and storage systems, including fuel cells and flow batteries. However, the practical application of membranes is significantly hindered by their limited conductivity and stability under strong alkaline conditions. Herein, a unique composite membrane decorated with functional Cu2+ cross-linked chitosan (Cts-Cu-M) is reported and their high hydroxide ion conductivity and stability in alkaline flow batteries are demonstrated. The underlying hydroxide ions transport of the membrane through Cu2+ coordinated nano-confined channels with abundant hydrogen bonding network via Grotthuss (proton hopping) mechanism is proposed. Consequently, the Cts-Cu-M membrane achieves high hydroxide ion conductivity with an area resistance of 0.17Ωcm2 and enables an alkaline zinc-based flow battery to operate at 320mAcm-2, along with an energy efficiency of ≈80%. Furthermore, the membrane enables the battery for 200cycles of long-cycle stability at a current density of 200mAcm-2. This study offers an in-depth understanding of ion transport for the design and preparation of high-performance membranes for energy storage devices and beyond.

Redox-Active Boron Clusters.

ConspectusIn this Account, we discuss our group's research over the past decade on a class of functionalized boron clusters with tunable chemical and physical properties, with an emphasis on accessing and controlling their redox behavior. These clusters can be thought of as three-dimensional aromatic systems that have distinct redox behavior and photophysical properties compared to their two-dimensional organic counterparts. Specifically, our lab has studied the highly tunable, multielectron redox behavior of B12(OR)12 clusters and applied these molecules in various settings. We first discuss the spectroscopic and electrochemical characterization of B12(OR)12 clusters in various oxidation states, followed by their use as catholytes and/or anolytes in redox flow batteries and chemical dopants in conjugated polymers. Additionally, the high oxidizing potential and visible light-absorbing nature of fluoroaryl-functionalized B12(OR)12 clusters have been leveraged by our group to generate weakly coordinating, photoexcitable species that can promote photooxidation chemistry.We have further translated these solution-phase studies of B12(OR)12 clusters to the solid state by using the precursor [B12(OH)12]2- cluster as a robust building block for hybrid metal oxide materials. Specifically, we have shown that the boron cluster can act as a thermally stable cross-linking material, which enhances electron transport between metal oxide nanoparticles. We applied this structural motif to create TiO2- and WO3-containing materials that showed promising properties as photocatalysts and electroactive materials for supercapacitors. Building on this concept, we later discovered that B12(OCH3)12, the smallest of the B12(OR)12 family, could retain its redox behavior in the solid state, a previously unseen phenomenon. We successfully harnessed this unique behavior for solid-state energy storage by implementing this boron cluster as a cathode-active material in a Li-ion prototype cell device. Recently, our group has also explored how to tune the redox properties of clusters other than B12(OR)12 species by synthesizing a library of vertex-differentiated clusters containing both B-OR and B-halogen groups. Due to the additive qualities of different functional groups on the cluster, these species allow access to a region of electrochemical potentials previously inaccessible by fully substituted closo-dodecaborate alkoxy-based derivatives.Lastly, we discuss our research into smaller-sized redox-active polyhedral boranes (B6- and B10-based cluster cores). Interestingly, these clusters show significantly less redox stability and reversibility than their dodecaborate-based counterparts. While exploring the functionalization of closo-hexaborate to create fully substituted derivates (i.e., [B6R6Hfac]-), we observed unique oxidative decomposition pathways for this cluster system. Consequently, we leveraged this oxidative instability to generate useful alkyl boronate esters via selective chemical oxidation. We further explored a closo-decaborate cluster as a platform to access electrophilic [B10H13]+ species capable of directly borylating arene compounds with unique regioselectivity. Upon chemical oxidation of the arylated decaborate clusters, we successfully synthesized various aryl boronate esters, establishing the generality of the oxidative cluster deconstruction concept.Overall, our work shows that boron clusters are an appealing class of redox-active molecules, and this fundamental and understudied property can be leveraged for constructing novel materials with tunable physical and electrochemical properties, as well as producing unique chemical reagents for small molecule synthesis.

Electrochemical Deposition of Bismuth on Graphite Felt Electrodes: Influence on Negative Half-Cell Reactions in Vanadium Redox Flow Batteries

In this paper, bismuth (Bi) was successfully deposited on graphite felts to improve the electrochemical performances of vanadium redox flow batteries. Modified graphite felts with different Bi particle loadings were obtained through electrochemical deposition at voltages of 0.8 V, 1.2 V and 1.6 V in 0.1 M BiCl3 solution for 10 min. The optimal Bi particle loading was confirmed by scanning electron microscopy (SEM), single cells and electrochemical tests. The SEM images revealed the deposition of granular Bi particles on the fiber surface. The Bi-modified felts which were electro-chemically deposited at 1.2 V (Bi/TGF-1.2V) showed excellent electrochemical performances in cyclic voltammetry curves and impedance spectroscopy. Meanwhile, the single cells assembled with Bi/TGF-1.2V as negative electrodes exhibited higher voltage efficiencies than the others. The optimized Bi particle loading induced better catalysis of the V3+/V2+ reaction and hence significantly improved the cell performances. In addition, the prepared Bi-modified felts showed stable cell performances and slower charge–discharge capacity declines than the other electrodes at current densities between 20 mA/cm2 and 80 mA/cm2. Compared with the pristine felt, the voltage efficiency of the vanadium redox flow battery assembled with Bi/TGF-1.2V graphite felt was 9.47% higher at the current density of 80 mA/cm2. The proposed method has considerable potential and guiding significance for the future modification of graphite felt for redox flow batteries.

In Situ Determination of the Potential Distribution within a Copper Foam Electrode in a Zinc‐Air/Silver Hybrid Flow Battery

AbstractThis work describes a novel methodology for measuring the potential distribution within the porous copper foam electrode of a zinc‐air/silver hybrid (ZASH) flow battery by using local potential probes. The suitability of dynamic hydrogen electrodes (DHEs) and a quasi‐reference electrode as probes is evaluated, with the latter chosen in view of stability. Liquid and solid‐phase potentials are recorded at varying applied current densities over multiple charge‐discharge cycles. Various zinc structures are found within specific overpotential ranges, with moss‐like structures appearing between 7.8 mV and 13.2 mV and the desired boulder structures in the range of 22 mV to 100 mV. Regardless of the current density, the highest liquid‐phase potentials are always measured in the outermost region of the porous foam near to the separator. In practice, this means that increasing the thickness of the copper foam over about 5 mm does not provide significant performance benefits. Conversely, solid‐phase potentials across the copper foam remain nearly uniform, resulting in negligible effects on local overpotential. The presented technique provides unique insights into the behavior of porous electrodes in electrochemical energy conversion technologies, facilitating the determination of the optimal properties for maximum efficiency, such as electrode thickness.

Anion exchange membrane based on poly(arylene ether sulfone)s functionalized with quinuclidinium-piperidinium dual cations for vanadium redox flow battery applications

Vanadium redox flow batteries (VRFBs) have gained significant interest as a prospective energy storage solution due to their scalability and extended cycle durability. The efficient functioning of VRFBs relies significantly on anion exchange membranes (AEMs), which facilitate the selective transport of ions while preventing crossover. In this study, we present a novel AEM based on poly(arylene ether sulfone)s (PAES) functionalized with dual cations (quinuclidinium-piperidinium) (DC-PAES) bearing a butyl spacer, explicitly designed for VRFB applications. The DC-PAES membrane containing dual cations separated by a butyl spacer results in a balanced combination of hydrophilicity and hydrophobicity, which enables efficient ion transport across the membrane. The DC-PAES membrane showed hydroxide conductivity of 0.085 S/cm at 80 °C, having an ion exchange capacity (IEC) of 1.42 mmol/g. The resulting DC-PAES membrane displayed low permeability (2.1 × 10−7 cm2 min−1) and high selectivity (12.3 × 105 S min cm−3) to vanadium. The performance of the AEMs fabricated for VRFB application showed better Coulombic (97.1 %), energy (90.0 %), and voltage efficiency (92.63 %) at 40 mAcm−2 higher than Nafion 117. The reported AEMs revealed excellent stability due to the steric and ring constraints of quinuclidinium and piperidinium cation, hindering the attack of oxidative species. Furthermore, the DC-PAES membrane demonstrated improved battery cycling performance lasting up to 150 cycles under in-situ conditions, making it a promising separator material for VRFB applications.

Commercializable Naphthalene Diimide Anolytes for Neutral Aqueous Organic Redox Flow Batteries

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate the transition of renewable energy sources from auxiliary to primary energy, the commercial production of anolyte materials still suffers from insufficient performance of high‐concentration and the high cost of the preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology and introduces the charged functional groups into hydrophobic naphthalene diimide cores, and prepares a series of high‐performance naphthalene diimide anolytes. Under the synergistic effect of π‐π stacking and H‐bonding networks, the naphthalene diimide exhibits excellent structural stability and the highest water solubility (1.85 M for dex‐NDI) reported to date. By employing the hydrothermal method, low‐cost naphthalene diimides are successfully synthesized on a hundred‐gram scale of $0.16 g‐1 ($2.43 Ah‐1), which is also the lowest price reported to date. The constructed full battery achieves a high electron concentration of 2.4 M, a high capacity of 54.4 Ah L‐1, and a power density of 318 mW cm‐2 with no significant capacity decay observed during long‐duration cycling. These findings provide crucial support for the commercialization of AORFBs and pave the way for revolutionary developments in neutral AORFBs.

Commercializable Naphthalene Diimide Anolytes for Neutral Aqueous Organic Redox Flow Batteries.

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate the transition of renewable energy sources from auxiliary to primary energy, the commercial production of anolyte materials still suffers from insufficient performance of high-concentration and the high cost of the preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology and introduces the charged functional groups into hydrophobic naphthalene diimide cores, and prepares a series of high-performance naphthalene diimide anolytes. Under the synergistic effect of π-π stacking and H-bonding networks, the naphthalene diimide exhibits excellent structural stability and the highest water solubility (1.85 M for dex-NDI) reported to date. By employing the hydrothermal method, low-cost naphthalene diimides are successfully synthesized on a hundred-gram scaleof $0.16 g-1 ($2.43 Ah-1), which is also the lowest price reported to date. The constructed full battery achieves a high electron concentration of 2.4 M, a high capacity of 54.4 Ah L-1, and a power density of 318 mW cm-2 with no significant capacity decay observed during long-duration cycling. These findings provide crucial support for the commercialization of AORFBs and pave the way for revolutionary developments in neutral AORFBs.

An Innovative Concept of Membrane-Free Redox Flow Batteries with Near-Zero Contact Distance Between Electrodes.

Given that the ion-exchange membrane takes up more than 30% of redox flow battery (RFB) cost, considerable cost reduction is anticipated with the membrane-free design. However, eliminating the membrane/separator would expose the membrane-free RFBs to a higher risk of short-circuits, and the dendrite growth may aggravate this issue. The current strategy based on expanding distances between electrodes is proposed to address short-circuit issues. Nevertheless, this approach would decrease the energy efficiency (EE) and could not restrain dendrite growth fundamentally. Herein, an inexpensive and electron-insulating boron nitride nanosheets (BNNSs)-Nylon hybrid interlayer (BN/Nylon) is developed for general membrane-free RFBs to achieve "near-zero distance" contact between electrodes. And the Lewis acid sites (B atoms) in BNNS can interact with the Lewis base anions in electrolytes, enabling a reduced Pb2+concentration gradient. Additionally, the ultrahigh thermal conductivity and mechanical strength of BNNSs promote the uniform plating/stripping process of Pb and PbO2. Compared with conventional soluble lead RFBs, introducing BN/Nylon interlayers boosts EE by ≈38.2% at 25mAcm-2, and extends the cycle life to 100 cycles. This innovative strategy premieres the application of the BN/Nylon interlayer concept, offering a novel perspective for the development of general membrane-free RFBs.

Vanadium-Mediated High Areal Capacity Zinc–Manganese Redox Flow Battery

Vanadium-Mediated High Areal Capacity Zinc–Manganese Redox Flow Battery

Cascaded Fractional-Order Controller-Based Load Frequency Regulation for Diverse Multigeneration Sources Incorporated with Nuclear Power Plant

To sustain a system frequency within acceptable limits, it is widely conceded that retaining a power balance between generation and demand is necessary. In order to regulate the frequency of power systems (PSs) this article proposes a novel cascaded based fractional-order controller termed as fractional-order integer- (FOI-) fractional-order proportional integral with double derivative (FOPIDD2). In addition to redox flow batteries and capacitive energy storage, the recommended control strategy has been validated with gas, thermal reheat, hydro, and nuclear power systems. Additionally, a newly designed algorithm known as squid game optimizer (SGO) optimizes the gains of the new FOI-FOPIDD2 controller. The squid game optimizer technique is inspired by the fundamental principles of a conventional Korean sport. It employs a population of candidate solutions and iteratively adjusts the control parameters to discover the optimal set that reduces frequency abnormalities and improves system stability. A comparison is also made between the controller’s performance and benchmarks, including the jellyfish search algorithm, the firefly algorithm, the grey wolf optimizer, and the particle swarm algorithm. The proposed algorithms reduced peak overshoot as compared to grey wolf optimizer algorithm by 35.34%, 46.78%, and 76.89%; jellyfish search optimization algorithm by 34.76%, 77.22%, and 82.56%; and firefly algorithm by 82.67%, 89.23%, and 29.67% for frequency variations in area 1, area 2 and tie line power, respectively. Furthermore, SGO-FOI-FOPIDD2 controllers under different loading circumstances and conditions were evaluated and endorsed for their ability to withstand uncertainties in power system parameters.

Potential prediction in aqueous organic redox-targeting flow batteries: DFT calculation and experimental validation

Aqueous organic redox flow batteries (AORFBs) face challenges of low energy density, which can be addressed by the strategy of redox-targeting (RT) reaction integrating solid materials (SMs) with redox mediators (RMs). However, the potential matching between SM and RM is demanding and complex. In this work, we establish a precise density functional theory (DFT) protocol to predict redox potential in RT-AORFB with anthraquinone-2,7-disulfonic acid (AQDS) derivatives as RM and poly(N-anthraquinoyl pyrrole) (PAQPy) as SM. Theoretical redox potentials are calculated from the Gibbs free energy (GFE) of various molecular models. The results suggest a precise potential match for 1,8-dihydroxyanthraquinone-2,7-disulfonic acid (1,8-DHAQDS) and PAQPy (-1.08 V and -1.09 V vs. SHE). Additionally, hydrogen bonding is involved to make simulation results more realistic, demonstrating a positive potential shift with increased GFE difference for both AQDS derivatives and PAQPy. To further elucidate the influencing mechanism of hydrogen bonding, electrostatic potential (ESP) and HOMO-LUMO gap are integrated together with GFE. The results indicate the introduction of hydrogen bonding results in extended distance for electron tunneling and a larger HOMO-LUMO gap, leading to higher GFE difference and a positive potential shift. Remarkably, results of experimental validations agree well with theoretical potential calculation. Based on predictions results, the RT-AORFB is successfully constructed with the well-matched 1,8-DHAQDS and PAQPy, exhibiting a 3.86-fold capacity enhancement compared to blank AORFB with 1,8-DHAQDS. The integrated DFT approach with GFE, ESP and HOMO-LUMO gap in this work emerges as a promising method for accurately predicting redox potentials in RT systems.

Porous Ceramic Metal‐Based Flow Battery Composite Membrane

AbstractIn metal‐based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub‐10‐nm‐thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc‐iron flow battery prepared using this membrane achieved an outstanding energy efficiency of >80%, exhibiting excellent long‐term stability (over 1000 h) and extremely high areal capacity (260 mAh cm−2). Low‐field nuclear magnetic resonance (NMR) spectroscopy, small‐angle X‐ray scattering, in situ infrared spectroscopy, solid‐state NMR analysis, and nano‐computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next‐generation metal‐based flow battery membranes for energy and power generation.

An All-Soluble Fe/Mn-Based Alkaline Redox Flow Battery System.

Redox flow batteries (RFBs) are membrane-separated rechargeable flow cells with redox electrolytes, offering the potential for large-scale energy storage and supporting renewable energy grids. Yet, creating a cost-effective, high-performance RFB system is challenging. In this work, we investigate an Fe/Mn RFB alkaline system based on the [(TEA)Fe-O-Fe(TEA)]3-/4- and MnO4-/2- redox couples with a theoretical cell voltage of ∼1.43 V. This combination has not been systematically studied previously, but it can lead to a very low-cost and sustainable materials for high energy storage. Constant current cycling tests were performed at ±41 mA cm-22 between 20% and 80% SOC over 800 h (400 cycles) with an apparent Coulombic efficiency (CE) approaching 100%, while the voltage efficiency (VE) gradually decreased from ∼75.3% to ∼61.4% due to increasing internal resistances. The voltage efficiency loss can be mitigated through a periodic acid treatment to remove MnO2 deposits from the separator.

Porous Ceramic Metal-Based Flow Battery Composite Membrane.

In metal-based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub-10-nm-thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc-iron flow battery prepared using this membrane achieved an outstanding energy efficiency of >80%, exhibiting excellent long-term stability (over 1000 h) and extremely high areal capacity (260 mAh cm-2). Low-field nuclear magnetic resonance (NMR) spectroscopy, small-angle X-ray scattering, in situ infrared spectroscopy, solid-state NMR analysis, and nano-computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next-generation metal-based flow battery membranes for energy and power generation.

Macrocycle-based covalent-organic-polymer as efficient oxygen electrocatalysts for zinc-air flow batteries

Covalent organic polymers (COPs), as emerging porous materials with well-defined architectures and high hydrothermal stability, have attracted extensive attention in the field of electrocatalysis. Herein, we report a rational design method for preparing oxygen reduction reaction electrocatalysts with the assistance of a predesigned macrocyclic COP model molecular. With the predesigned nitrogen position and structural features in macrocyclic chain-like COP-based materials, the obtained COPMCT-Co-900 catalyst provided excellent oxygen reduction performance, where the half-wave potential (E1/2) reaches 0.85 V (vs . RHE), comparable to commercial Pt/C. We also extended the strategy to similar macrocycle COPs and Fe-based and Ni-based metal sources and studied the oxygen reduction reaction performance of corresponding catalysts, proving the universality of the method. Interestingly, we assemble COPMCT-Co-900 catalyst as air electrode catalyst of the self-made rechargeable zinc-air flow batteries, which exhibit outstanding power density (155.6 mW·cm-2) and long cycle life (90 h, 270 cycles at 10 mA·cm-2). Our studies provide a new method for the development of high-performance oxygen electrodes applied in zinc-air flow battery devices.

A Highly Integrated Component with Tri‐Part Significantly Enhances Fuel Cell Power Density by Reducing Mass Transfer Resistance and Excellent Humidity Tolerance

AbstractTraditional flow fields and gas diffusion layers (GDL) suffer from water flooding at the rib contact surface, resulting in mass transfer obstruction. Herein, an integrated component (i‐component) with tri‐part of the flow field, gas diffusion backing, and the microporous layer is prepared using the filter molding method to prevent flooding at the rib. The i‐component with micro‐tunnels is more compact than traditional fuel cells and has no distinct interface, significantly enhancing fuel cell performance, reducing mass transfer resistance, and improving water management. Remarkably, the mass transfer resistance of the i‐components is reduced by six times, accompanied by a 50% increase in power density (1.63 W cm−2) and a 146% surge in volume‐specific power (24 500 W L−1). Additionally, it exhibits excellent humidity tolerance in the relative humidity range of 30–100%. This method achieves large‐area i‐component (388 cm2) preparation in 0.5 h at 350 °C, which reduces time by dozens and energy consumption by over 100 times compared to the traditional method for preparing commercial GDL. The i‐component significantly enhances the mass transfer and water management capabilities of fuel cells. Hence, the i‐component provides new strategies for next‐generation fuel cells, water electrolysis, flow battery, carbon dioxide reduction, etc.

Recent Advances and Opportunities in Reactivating Inactive Lithium in Batteries

The loss of active materials is one of the main culprits of the battery failures. As a typical example, the presence of inactive lithium, also known as “dead lithium”, contributes to the rapid capacity deterioration and reduces energy output in lithium batteries. This phenomenon has long been recognized as irreversible. In this Minireview, the first of this kind, we aim to summarize the formation of inactive lithium and reassess its impact on battery performance metrics. Additionally, we explore various strategies that have been devised to rejuvenate inactive lithium. This comprehensive overview of the latest advancements in reactivating inactive lithium not only offers insights into restoring capacity and enhancing battery performance metrics but also provides a foundation for future research in reviving other inactive materials found in next‐generation batteries, such as lithium metal, lithium‐sulfur, silicon, and liquid flow batteries.

Recent Advances and Opportunities in Reactivating Inactive Lithium in Batteries.

The loss of active materials is one of the main culprits of the battery failures. As a typical example, the presence of inactive lithium, also known as "dead lithium", contributes to the rapid capacity deterioration and reduces energy output in lithium batteries. This phenomenon has long been recognized as irreversible. In this Minireview, the first of this kind, we aim to summarize the formation of inactive lithium and reassess its impact on battery performance metrics. Additionally, we explore various strategies that have been devised to rejuvenate inactive lithium. This comprehensive overview of the latest advancements in reactivating inactive lithium not only offers insights into restoring capacity and enhancing battery performance metrics but also provides a foundation for future research in reviving other inactive materials found in next-generation batteries, such as lithium metal, lithium-sulfur, silicon, and liquid flow batteries.

Leveraging Temperature-Dependent (Electro)Chemical Kinetics for High-Throughput Flow Battery Characterization

The library of redox-active organics that are potential candidates for electrochemical energy storage in flow batteries is exceedingly vast, necessitating high-throughput characterization of molecular lifetimes. Demonstrated extremely stable chemistries require accurate yet rapid cell cycling tests, a demand often frustrated by time-denominated capacity fade mechanisms. We have developed a high-throughput setup for elevated temperature cycling of redox flow batteries, providing a new dimension in characterization parameter space to explore. We utilize it to evaluate capacity fade rates of aqueous redox-active organic molecules, as functions of temperature. We demonstrate Arrhenius-like behavior in the temporal capacity fade rates of multiple flow battery electrolytes, permitting extrapolation to lower operating temperatures. Collectively, these results highlight the importance of accelerated decomposition protocols to expedite the screening process of candidate molecules for long lifetime flow batteries.

A Non-Stabilized Supersaturated High-Energy-Density Storage Concept for the Redox Flow Battery and Its Demonstration in an H2-V System

Redox Flow Batteries are ideal for grid-scale energy storage but have low energy density. In an effort to resolve this issue, this work presents an H2-vanadium RFB system that operates with the catholyte above the solubility limit of vanadium ions in the supersaturated regime without the use of chemical stabilizers, necessary for the operation of a novel solid/liquid storage concept. Initial charge/discharge testing was performed at constant potential (1.35 V charge and 0.65 V discharge) increasing Vanadium concentrations from 1.5 M to 2.5 M. Coulometric capacity increased 67% (40.2 Ah l−1 to 67.0 Ah l−1) while average current density decreased 35% (48 mA cm−2 to 31 mA cm−2) with charge/discharge limited to SOC (20%–80%). Continuing charge/discharge with a cutoff current of 5.56 mA cm−2 increased coulombic capacity by 43% (36.4 Ah l−1 to 51.9 Ah l−1) while average current density decreased 17% (27.7 mA cm−2 to 22.9 mA cm−2). Additional testing was performed with constant current charge/discharge (75 mA cm−2), limited by cutoff potential (1.35 V charge and 0.60 V discharge). Coulometric capacity increased 73.5% (26.5 Ah l−1 to 46.0 Ah l−1) with higher working potential for the 2.5 M Vanadium solution. Energy capacity increased 79.1% (25.3 Wh l−1 to 45.3 Wh l−1) with minimal change in charge/discharge power (90.7/−70.9 mW cm−2 to 92.1/−72.8 mW cm−2) and efficiency (77.1% to 78.4%).