Near Neutral pH Redox Flow Battery with Low Permeability and Long‐Lifetime Phosphonated Viologen Active Species

A highly stable phosphonate‐functionalized viologen is introduced as the redox‐active material in a negative potential electrolyte for aqueous redox flow batteries (ARFBs) operating at nearly neutral pH. The solubility is 1.23 m and the reduction potential is the lowest of any substituted viologen utilized in a flow battery, reaching ?0.462 V versus SHE at pH = 9. The negative charges in both the oxidized and the reduced states of 1,1′‐bis(3‐phosphonopropyl)‐[4,4′‐bipyridine]‐1,1′‐diium dibromide ( BPP?Vi ) effect low permeability in cation exchange membranes and suppress a bimolecular mechanism of viologen decomposition. A flow battery pairing BPP?Vi with a ferrocyanide‐based positive potential electrolyte across an inexpensive, non‐fluorinated cation exchange membrane at pH = 9 exhibits an open‐circuit voltage of 0.9 V and a capacity fade rate of 0.016% per day or 0.00069% per cycle. Overcharging leads to viologen decomposition, causing irreversible capacity fade. This work introduces extremely stable, extremely low‐permeating and low reduction potential redox active materials into near neutral ARFBs.     

An All‐Organic Non‐aqueous Lithium‐Ion Redox Flow Battery

A non‐aqueous lithium‐ion redox flow battery employing organic molecules is proposed and investigated. 2,5‐Di‐tert‐butyl‐1,4‐bis(2‐methoxyethoxy)benzene and a variety of molecules derived from quinoxaline are employed as initial high‐potential and low‐potential active materials, respectively. Electrochemical measurements highlight that the choice of electrolyte and of substituent groups can have a significant impact on redox species performance. The charge‐discharge characteristics are investigated in a modified coin‐cell configuration. After an initial break‐in period, coulombic and energy efficiencies for this unoptimized system are ～70% and ～37%, respectively, with major charge and discharge plateaus between 1.8‐2.4 V and 1.7‐1.3 V, respectively, for 30 cycles. Performance enhancements are expected with improvements in cell design and materials processing.     

Comparison of Quinone‐Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long‐Term Stability with Tetrasubstituted Quinones

Quinones are appealing targets as organic charge carriers for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series of water‐soluble quinones, with redox potentials ranging from 605–885 mV versus NHE, under acidic aqueous conditions (1 m H₂SO₄). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone‐2,7‐disulfonate as the anodic electrolyte. The RFB data complement other solution stability tests and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improved organic electrolytes for aqueous RFBs.     

A High Voltage Aqueous Zinc–Organic Hybrid Flow Battery

Water‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)₄]^2? redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.     

A Long Lifetime Aqueous Organic Solar Flow Battery

Monolithically integrated solar flow batteries (SFBs) hold promise as compact stand‐alone energy systems for off‐grid solar electrification. Although considerable research is devoted to studying and improving the round‐trip efficiency of SFBs, little attention is paid to the device lifetime. Herein, a neutral pH aqueous electrolyte SFB with robust organic redox couples and inexpensive silicon‐based photoelectrodes is demonstrated. Enabled by the excellent stability of both electrolytes and protected photoelectrodes, this SFB device exhibits not only unprecedented stable continuous cycling performance over 200 h but also a capacity utilization rate higher than 80%. Moreover, through comprehensive study on the working mechanisms of SFBs, a new theory based on instantaneous solar‐to‐output electricity efficiency toward more optimized device design is developed and a significantly improved solar‐to‐output electricity efficiency of 5.4% from single‐junction silicon photoelectrodes is realized. The design principles presented in this work for extending device lifetime and boosting round trip energy efficiency will make SFBs more competitive for off‐grid applications.     

A High‐Energy‐Density Multiple Redox Semi‐Solid‐Liquid Flow Battery

A new concept of multiple redox semi‐solid‐liquid (MRSSL) flow battery that takes advantage of active materials in both liquid and solid phases, is proposed and demonstrated. Liquid lithium iodide (LiI) electrolyte and solid sulfur/carbon (S/C) composite, forming LiI‐S/C MRSSL catholyte, are employed to demonstrate this concept. Record volumetric capacity (550 Ah L^?1_catholyte) is achieved using highly concentrated and synergistic multiple redox reactions of LiI and sulfur. The liquid LiI electrolyte is found to increase the reversible volumetric capacity of the catholyte, improve the electrochemical utilization of the S/C composite, and reduce the viscosity of catholyte. A continuous flow test is demonstrated and the influence of the flow rate on the flow battery performance is discussed. The MRSSL flow battery concept transforms inactive component into bi‐functional active species and creates synergistic interactions between multiple redox couples, offering a new direction and wide‐open opportunities to develop high‐energy‐density flow batteries.     

A Phosphonate‐Functionalized Quinone Redox Flow Battery at Near‐Neutral pH with Record Capacity Retention Rate

A highly stable phosphonate‐functionalized anthraquinone is introduced as the redox‐active material in a negative potential electrolyte (negolyte) for aqueous redox flow batteries operating at nearly neutral pH. The design and synthesis of 2,6‐DPPEAQ, (((9,10‐dioxo‐9,10‐dihydroanthracene‐2,6‐diyl)bis(oxy))bis(propane‐3,1‐diyl))bis(phosphonic acid), which has a high solubility at pH 9 and above, is described. Chemical stability studies demonstrate high stability at both pH 9 and 12. By pairing 2,6‐DPPEAQ with a potassium ferri/ferrocyanide positive electrolyte across an inexpensive, nonfluorinated permselective polymer membrane, this near‐neutral quinone flow battery exhibits an open‐circuit voltage of 1.0 V and a capacity fade rate of 0.00036% per cycle and 0.014% per day, which is the lowest ever reported for any flow battery in the absence of rebalancing processes. It is further demonstrated that the negolyte pH drifts upward upon atmospheric oxygen penetration but, when oxygen is excluded, oscillates reversibly between 9 and 12 during cycling. These results enhance the suitability of aqueous‐soluble redox‐active organics for use in large‐scale energy storage, potentially enabling massive penetration of intermittent renewable electricity.     

Alkaline Benzoquinone Aqueous Flow Battery for Large‐Scale Storage of Electrical Energy

An aqueous flow battery based on low‐cost, nonflammable, noncorrosive, and earth‐abundant elements is introduced. During charging, electrons are stored in a concentrated water solution of 2,5‐dihydroxy‐1,4‐benzoquinone, which rapidly receives electrons with inexpensive carbon electrodes without the assistance of any metal electrocatalyst. Electrons are withdrawn from a second water solution of a food additive, potassium ferrocyanide. When these two solutions flow along opposite sides of a cation‐conducting membrane, this flow battery delivers a cell potential of 1.21 V, a peak galvanic power density of 300 mW cm^?2, and a coulombic efficiency exceeding 99%. Continuous cell cycling at 100 mA cm^?2 shows a capacity retention rate of 99.76% cycle^?1 over 150 cycles. Various molecular modifications involving substitution for hydrogens on the aryl ring are implemented to block decomposition by nucleophilic attack of hydroxide ions. These modifications result in increased capacity retention rates of up to 99.96% cycle^?1 over 400 consecutive cycles, accompanied by changes in voltage, solubility, kinetics, and cell resistance. Quantum chemistry calculations of a large number of organic compounds predict a number of related structures that should have even higher performance and stability. Flow batteries based on alkaline‐soluble dihydroxybenzoquinones and derivatives are promising candidates for large‐scale, stationary storage of electrical energy.     

Annulated Dialkoxybenzenes as Catholyte Materials for Non‐aqueous Redox Flow Batteries: Achieving High Chemical Stability through Bicyclic Substitution

1,4‐Dimethoxybenzene derivatives are materials of choice for use as catholytes in non‐aqueous redox flow batteries, as they exhibit high open‐circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring‐addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10‐bis(2‐methoxyethoxy)‐1,2,3,4,5,6,7,8‐octahydro‐1,4:5,8‐dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. A hybrid flow cell containing BODMA is operated for 150 charge–discharge cycles with a minimal loss of capacity.     

A New Fe/V Redox Flow Battery Using a Sulfuric/Chloric Mixed‐Acid Supporting Electrolyte

A redox flow battery using Fe²⁺/Fe³⁺ and V²⁺/V³⁺ redox couples in chloric/sulfuric mixed‐acid supporting electrolyte is investigated for potential stationary energy storage applications. The Fe/V redox flow cell using mixed reactant solutions operates within a voltage window of 0.5–1.35 V with a nearly 100% utilization ratio and demonstrates stable cycling over 100 cycles with energy efficiency >80% and no capacity fading at room temperature. A 25% improvement in the discharge energy density of the Fe/V cell is achieved compared with a previously reported Fe/V cell using a pure chloride acid supporting electrolyte. Stable performance is achieved in the temperature range between 0 and 50 °C as well as when using a microporous separator as the membrane. The improved electrochemical performance makes the Fe/V redox flow battery a promising option as a stationary energy storage device to enable renewable integration and stabilization of the electric grid.     

A Stable Vanadium Redox‐Flow Battery with High Energy Density for Large‐Scale Energy Storage

The all‐vanadium redox flow battery is a promising technology for large‐scale renewable and grid energy storage, but is limited by the low energy density and poor stability of the vanadium electrolyte solutions. A new vanadium redox flow battery with a significant improvement over the current technology is reported in this paper. This battery uses sulfate‐chloride mixed electrolytes, which are capable of dissolving 2.5 M vanadium, representing about a 70% increase in energy capacity over the current sulfate system. More importantly, the new electrolyte remains stable over a wide temperature range of ?5 to 50 °C, potentially eliminating the need for electrolyte temperature control in practical applications. This development would lead to a significant reduction in the cost of energy storage, thus accelerating its market penetration.     

Nanoporous Polytetrafluoroethylene/Silica Composite Separator as a High‐Performance All‐Vanadium Redox Flow Battery Membrane

A novel low‐cost nanoporous polytetrafluoroethylene (PTFE)/silica composite separator has been prepared and evaluated for its use in an all‐vanadium redox flow battery (VRB). The separator consists of silica particles enmeshed in a PTFE fibril matrix. It possesses unique nanoporous structures with an average pore size of 38 nm and a porosity of 48%. These pores function as the ion transport channels during redox flow battery operation. This separator provides excellent electrochemical performance in the mixed‐acid VRB system. The VRB using this separator delivers impressive energy efficiency, rate capability, and temperature tolerance. In additon, the flow cell using the novel separator also demonstrates an exceptional capacity retention capability over extended cycling, thus offering excellent stability for long‐term operation. The characteristics of low cost, excellent electrochemical performance and proven chemical stability afford the PTFE/silica nanoporous separator great potential as a substitute for the Nafion membrane used in VRB applications.     

High‐Performance Aqueous Rechargeable Li‐Ni Battery Based on Ni(OH)2/NiOOH Redox Couple with High Voltage

New energy storage and conversion systems require large‐scale, cost‐effective, good safety, high reliability, and high energy density. This study demonstrates a low‐cost and safe aqueous rechargeable lithium‐nickel (Li‐Ni) battery with solid state Ni(OH)₂/NiOOH redox couple as cathode and hybrid electrolytes separated by a Li‐ion‐conductive solid electrolyte layer. The proposed aqueous rechargeable Li‐Ni battery exhibits an approximately open‐circuit potential of 3.5 V, outperforming the theoretic stable window of water 1.23 V, and its energy density can be 912.6 W h kg^‐1, which is much higher than that of state‐of‐the‐art lithium ion batteries. The use of a solid‐state redox couple as cathode with a metallic lithium anode provides another postlithium chemistry for practical energy storage and conversion.