Person:

Tong, Liuchuan

Redox-flow batteries (RFBs) can store large amounts of electrical energy from variable sources, such as solar and wind. Recently, redox-active organic molecules in aqueous RFBs have drawn substantial attention due to their rapid kinetics and low membrane crossover rates. Drawing inspiration from nature, here we report a high-performance aqueous RFB utilizing an organic redox compound, alloxazine, which is a tautomer of the isoalloxazine backbone of vitamin B2. It can be synthesized in high yield at room temperature by single-step coupling of inexpensive o-phenylenediamine derivatives and alloxan. The highly alkaline-soluble alloxazine 7/8-carboxylic acid produces a RFB exhibiting open-circuit voltage approaching 1.2 V and current efficiency and capacity retention exceeding 99.7% and 99.98% per cycle, respectively. Theoretical studies indicate that structural modification of alloxazine with electron-donating groups should allow further increases in battery voltage. As an aza-aromatic molecule that undergoes reversible redox cycling in aqueous electrolyte, alloxazine represents a class of radical-free redox-active organics for use in large-scale energy storage.

We introduce an aqueous flow battery based on low-cost, non-flammable, non-corrosive and Earth-abundant elements. During charging, electrons are stored in a concentrated water solution of 2,5-dihydroxy-1,4-benzoquinone (DHBQ), which rapidly receives electrons with inexpensive carbon electrodes without the assistance of any metal electro-catalyst. Electrons are withdrawn from a second water solution of a food additive, potassium ferrocyanide (K4Fe(CN)6). 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/cm2 and a coulombic efficiency exceeding 99%. Continuous cell cycling at 100 mA/cm2 shows a capacity retention rate of 99.76%/cycle over 150 cycles. Various molecular modifications involving substitution for hydrogens on the aryl ring were implemented to block decomposition by nucleophilic attack of hydroxide ions in solution. These modifications resulted in increased capacity retention rates of up to 99.962%/cycle over 400 consecutive cycles, accompanied by changes in voltage, solubility, kinetics and cell resistance. Quantum chemistry calculations of a large number of organic compounds predicted 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.

Quinone-based aqueous flow batteries provide a potential opportunity for large-scale, low-cost energy storage due to their composition from earth abundant elements, high aqueous solubility, reversible redox kinetics and their chemical tunability such as reduction potential. In an operating flow battery utilizing 9,10-anthraquinone-2,7-disulfonic acid, the aggregation of an oxidized quinone and a reduced hydroquinone to form a quinhydrone dimer causes significant variations from ideal solution behavior and of optical absorption from the Beer-Lambert law. We utilize in-situ UV-Vis spectrophotometry to establish (a), quinone, hydroquinone and quinhydrone molar attenuation profiles and (b), an equilibrium constant for formation of the quinhydrone dimer (KQHQ) ~ 80 M-1. We use the molar optical attenuation profiles to identify the total molecular concentration and state of charge at arbitrary mixtures of quinone and hydroquinone. We report density functional theory calculations to support the quinhydrone UV-Vis measurements and to provide insight into the dimerization conformations. We instrument a quinone-bromine flow battery with a Pd-H reference electrode in order to demonstrate how complexation in both the negative (quinone) and positive (bromine) electrolytes directly impacts measured half-cell and full-cell voltages. This work shows how accounting for electrolyte complexation improves the accuracy of electrochemical modeling of flow battery electrolytes.

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 den- sity 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 perfor- mance and stability. Flow batteries based on alkaline-soluble dihydroxybenzo- quinones and derivatives are promising candidates for large-scale, stationary storage of electrical energy.

Aqueous organic redox flow batteries (AORFBs) have recently gained significant attention as a potential candidate for grid-scale electrical energy storage. Successful implementation of this technology will require redox-active organic molecules with many desired properties. Here we introduce a naphthoquinone dimer, bislawsone, as the redox-active material in a negative potential electrolyte (negolyte) for an AORFB. This novel dimerization strategy substantially improves the performance of the electrolyte vs. that of the lawsone monomer in terms of solubility, stability, reversible capacity, permeability and cell voltage. An AORFB pairing bislawsone with a ferri/ferrocyanide positive electrolyte delivers an open-circuit voltage of 1.05 V and cycles at a current density of 300 mA/cm2 with a negolyte concentration of 2 M electrons in alkaline solution. We determined the degradation mechanism for the naphthoquinone-based electrolyte using chemical analysis, and predict theoretically electrolytes based on naphthoquinones that will be even more stable.