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A redox-flow battery with an alloxazine-based organic electrolyte

Nature Energy volume 1, Article number: 16102 (2016) Cite this article

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Abstract

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.

Improved methods for storing electrical energy from intermittent renewable sources are needed to support the rapid deployment of photovoltaic and wind power1,2,3. A promising approach for safe and cost-effective stationary energy storage uses redox-flow batteries (RFBs), in which the energy is stored in fluids held outside the power conversion electrochemical cell4,5. This permits the independent engineering of energy (electrolyte volume and/or concentration) and power (cell area) capacities and enables the attainment of the high energy-to-power ratios (that is, long discharge durations at rated power) necessary to deliver energy from photovoltaics and wind when it is needed. Since the invention of RFBs in the 1970s, the development efforts for their electrolyte materials—the core component of RFBs—have concentrated on single metal ions such as vanadium, iron and chromium, where the battery voltages are fixed by the reduction potentials of these ions, and their solubilities and stabilities are governed by the pH and composition of the supporting electrolyte6,7. However, their development has been impeded by one or more shortcomings such as high electrolyte corrosivity, toxicity, cost, membrane crossover rate, or sluggish reaction kinetics.

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Figure 1: Cyclic voltammogram and cell schematic.
Figure 2: Cell performance.
Figure 3: Theoretical calculation and cyclic voltammetry of alloxazines.

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Acknowledgements

This work was funded by the US DOE ARPA-E award no. DE-AR0000348, NSF no. NSF-CBET-1509041, the Massachusetts Clean Energy Technology Center, and the Harvard John A. Paulson School of Engineering and Applied Sciences. We thank C. Qian for designing the Fig. 1d scheme. We appreciate support from the Odyssey Cluster and Research Computing of Harvard University’s Faculty of Arts and Sciences.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA

    Kaixiang Lin, Rafael Gómez-Bombarelli, Eugene S. Beh, Liuchuan Tong, Alán Aspuru-Guzik & Roy G. Gordon

  2. Harvard John A. Paulson School of Engineering and Applied Sciences, 29 Oxford Street, Cambridge, Massachusetts 02138, USA

    Eugene S. Beh, Qing Chen, Michael J. Aziz & Roy G. Gordon

  3. Harvard College, Cambridge, Massachusetts 02138, USA

    Alvaro Valle

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  1. Kaixiang Lin
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Contributions

K.L., R.G.G. and M.J.A. formulated the project. K.L. and L.T. synthesized the compounds. K.L., E.S.B. and L.T. collected and analysed the NMR data. K.L., Q.C., E.S.B. and A.V. collected and analysed the electrochemical data. K.L. and A.V. measured solubility. R.G.-B. and A.A.-G. performed theoretical analysis. K.L., R.G.G. and M.J.A. wrote the paper, and all authors contributed to revising the paper.

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Correspondence to Michael J. Aziz or Roy G. Gordon.

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The authors declare no competing financial interests.

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Supplementary Information

Supplementary Figures 1–13, Supplementary Table 1–2. (PDF 946 kb)

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Lin, K., Gómez-Bombarelli, R., Beh, E. et al. A redox-flow battery with an alloxazine-based organic electrolyte. Nat Energy 1, 16102 (2016). https://doi.org/10.1038/nenergy.2016.102

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