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  • The Electrochemical Society  (5)
  • Aziz, Michael J.  (5)
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  • The Electrochemical Society  (5)
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  • 1
    Online Resource
    Online Resource
    The Electrochemical Society ; 2023
    In:  ECS Meeting Abstracts Vol. MA2023-01, No. 3 ( 2023-08-28), p. 739-739
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2023-01, No. 3 ( 2023-08-28), p. 739-739
    Abstract: Aqueous Organic Redox Flow Batteries (AORFBs) have emerged as promising and potentially disruptive technologies for the storage of electrical energy from intermittent renewable sources for use over long discharge durations when the sun isn’t shining and the wind isn’t blowing. AORFBs could become preferred over Li-ion batteries for grid-scale stationary storage due to their potentially low-cost active materials made of earth-abundant elements, their inherent non-flammability, and the intrinsic decoupling of energy and power capacities in the flow battery design. Our group has demonstrated that calendar life, rather than cycle life, limits molecular lifetimes in AORFBs due to various molecular instabilities that lead to side reactions, thus inhibiting performance [1] . To accurately determine molecular fade rates, we utilize potentiostatic cycling to avoid artifacts caused by drifts in internal resistance and employ volumetrically unbalanced, compositionally symmetric cell configurations to distinguish molecular fade from membrane crossover or cell unbalancing. Redox-active organic molecule stability has improved to the point that the most stable chemistries degrade at less than 1% per year [2]. With further lifetime increases, the measurement of lower capacity fade rates necessitates higher precision coulometry methods [3] and thermally accelerated degradation protocols [4] to determine which stabilizing approaches are most effective without waiting for multi-month cycling tests to quantify capacity fade. We have developed a high-throughput setup for cycling AORFBs at elevated temperatures, providing a new dimension in the flow battery characterization space to explore. Capacity fade rates of previously published redox-active organic molecules, as functions of temperature, are evaluated in the high-throughput setup providing the ability to extrapolate fade rates to lower operating temperatures. The effect of temperature on electrochemical regeneration [5,6] of decomposed organic molecules is also explored. Collectively, these results highlight the importance of accelerated decomposition protocols to expedite the screening process of candidate molecules for long lifetime AORFBs, which may enable massive grid penetration of intermittent renewable energy. [1] M.-A. Goulet and M. J. Aziz, “Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods,” Journal of The Electrochemical Society , 165 , A1466 (2018). [2] M. Wu, Y. Jing, A. A. Wong, E. M. Fell, S. Jin, Z. Tang, R. G. Gordon, M. J. Aziz, “Extremely Stable Anthraquinone Negolytes Synthesized from Common Precursors,” Chem , 6 , 1432 (2020). [3] T. M. Bond, J. C. Burns, D. A. Stevens, H. M. Dahn, J. R. Dahn, "Improving Precision and Accuracy in Coulombic Efficiency Measurements of Li-Ion Batteries", Journal of The Electrochemical Society , 160 , A521 (2013). [4] D. A. Stevens, R. Y. Ying, R. Fathi, J. N. Reimers, J. E. Harlow, J. R. Dahn, "Using High Precision Coulometry Measurements to Compare the Degradation Mechanisms of NMC/LMO and NMC-Only Automotive Scale Pouch Cells", Journal of The Electrochemical Society , 161 , A1364 (2014). [5] M. Wu, M. Bahari, E. M. Fell, R. G. Gordon, M. J. Aziz, “High-performance anthraquinone with potentially low cost for aqueous redox flow batteries”, Journal of Materials Chemistry A , 9 , 26709 (2021). [6] Y. Jing, E. W. Zhao, M.-A. Goulet, M. Bahari, E. M. Fell, S. Jin, A. Davoodi, E. Jónsson, M. Wu, C. P. Grey, R. G. Gordon, M. J. Aziz, “ In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries,” Nature Chemistry , 14 , 1103, (2022). Figure caption: Capacity fade rates of an anthraquinone derivative, measured in symmetric cells, as a function of temperature. Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2023
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  • 2
    Online Resource
    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-02, No. 6 ( 2019-09-01), p. 524-524
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-02, No. 6 ( 2019-09-01), p. 524-524
    Abstract: Lithium-ion batteries continue to dominate portable electronics and electric vehicles markets for its high energy density/specific energy. 1 However, combustible electrolytes and expensive cathodes pose safety and cost concerns to consumers. 2 Further cost reduction is expected to be limited after decades of development. 3 Next generation energy storage devices call for safe, cheap, resource-abundant and flexible batteries. 2, 4 Rechargeable batteries with cost-effective redox active materials and aqueous electrolytes can potentially meet these requirements. 5 Aqueous battery chemistries include lead-acid batteries, nickel-metal hydride aqueous batteries, and emerging aqueous lithium/sodium-ion batteries, but they all have their Achilles’ heels. 6 - 12 Here we report a symmetric all-quinone aqueous battery based entirely on Earth-abundant elements that uses a naturally-occurring dye as the redox-active material in both positive and negative electrodes. We demonstrate a symmetric all-quinone cell with 1.04 V of open circuit voltage, 163 mAh/g of capacity, and 100 cycles at 10C with 100% of depth of discharge. The use of the same quinone in a symmetric setup expands the repertoire of inexpensive redox active materials for aqueous rechargeable batteries, and the simple cell design will enable optimizations toward safe, cheap, lightweight, and flexible electronics in the future. Natural abundance and cheap commercial source promise its low cost when produced at large scale. In addition, we demonstrate that other fused quinone derivatives can also be used for symmetric quinone-acid batteries. Further optimization of fused quinones with improved reduction potential and stability, and cell engineering of electrode composition and morphology can further improve the performance of the battery. References Zubi, G.; Dufo-López, R.; Carvalho, M.; Pasaoglu, G., The lithium-ion battery: State of the art and future perspectives. Renewable and Sustainable Energy Reviews 2018, 89 , 292-308. Armand, M.; Tarascon, J. M., Building better batteries. Nature 2008, 451 , 6. Hsieh, I.-Y. L.; Pan, M. S.; Chiang,Y.-M.; and Green, W. H. Learning only buys you so much: practical limits on battery price reduction Applied Energy 2019 , 239 , 218. Larcher, D.; Tarascon, J. M., Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 2015, 7 (1), 19-29. Beck, F.; Rüetschi, P., Rechargeable batteries with aqueous electrolytes. Electrochimica Acta 2000, 45 , 16. Chen, H. Y.; Li, A. J.; Finlow, D. E., The lead and lead-acid battery industries during 2002 and 2007 in China. Journal of Power Sources 2009, 191 (1), 22-27. van der Kuijp, T.; Huang, L.; Cherry, C. R., Health hazards of China's lead-acid battery industry: a review of its market drivers, production processes, and health impacts. Environmental Health 2013, 12 (61), 10. Ruetschi, P., Aging mechanisms and service life of lead–acid batteries. Journal of Power Sources 2004, 127 (1-2), 33-44. Zou, X., Kang, Zongxuan, Shu, Dong, Liao, Yuqing, Gong, Yibin, He, Chun, Hao, Junnan, Zhong, Yayun, Effects of carbon additives on the performance of negative electrode of lead-carbon battery. Electrochimica Acta 2015, 151 , 89-98. Rodrigues, L. E. O. C.; Mansur, M. B., Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel–metal–hydride batteries. Journal of Power Sources 2010, 195 (11), 3735-3741. Ying, T. K.; Gao, X. P.; Hu, W. K.; Wu, F.; Noréus, D., Studies on rechargeable NiMH batteries. Int. J. Hydrogen Energy 2006, 31 (4), 525-530. Kim, H.; Hong, J.; Park, K. Y.; Kim, H.; Kim, S. W.; Kang, K., Aqueous rechargeable Li and Na ion batteries. Chem. Rev. 2014, 114 (23), 11788-827. Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 3
    Online Resource
    Online Resource
    The Electrochemical Society ; 2018
    In:  ECS Meeting Abstracts Vol. MA2018-01, No. 1 ( 2018-04-13), p. 22-22
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2018-01, No. 1 ( 2018-04-13), p. 22-22
    Abstract: The use of quinone/hydroquinone couples in aqueous redox flow batteries is a promising pathway toward cost-effective stationary electrical energy storage [1]-[4] . A major remaining challenge is long-term molecule stability. We previously reported a record capacity-retention rate in a flow battery utilizing substituted viologens and ferrocenes [5]; however, the open-circuit voltage was only about 0.7 V. Here we report a novel quinone-based aqueous redox flow battery with an open circuit voltage of 1.0 V and a capacity-retention rate that sets new records for cycling in the absence of rebalancing procedures. At the time this abstract is being submitted, capacity fade extrapolates to roughly 2%/year while cycling for days at approximately 110 cycles/day. [1] B. Huskinson, M.P. Marshak, C. Suh, S. Er, M.R. Gerhardt, C.J. Galvin, X. Chen, A. Aspuru-Guzik, R.G. Gordon and M.J. Aziz, “A metal-free organic-inorganic aqueous flow battery”, Nature 505 , 195 (2014). [2] K. Lin, Q. Chen, M.R. Gerhardt, L. Tong, S.B. Kim, L. Eisenach, A.W. Valle, D. Hardee, R.G. Gordon, M.J. Aziz and M.P. Marshak, "Alkaline Quinone Flow Battery", Science 349 , 1529 (2015). [3] L. Hoober-Burkhardt, S. Krishnamoorthy, B. Yang, A. Murali, A. Nirmalchandar, G.K. Surya Prakash, and S.R. Narayanan, "A New Michael-Reaction-Resistant Benzoquinone for Aqueous Organic Redox Flow Batteries", Journal of the Electrochemical Society 164 , A600 (2017). [4] Z. Yang, L. Tong, D.P. Tabor, E.S. Beh, M.-A. Goulet, D. De Porcellinis, A. Aspuru-Guzik, R.G. Gordon, and M.J. Aziz, "Alkaline benzoquinone aqueous flow battery for large-scale storage of electrical energy” Advanced Energy Materials 7 , in press (2017). [5] E.S. Beh, D. De Porcellinis, R.L. Gracia, K.T. Xia, R.G. Gordon, and M.J. Aziz, "A Neutral pH Aqueous Organic–Organometallic Redox Flow Battery with Extremely High Capacity Retention", ACS Energy Letters 2 , 639 (2017).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2018
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  • 4
    Online Resource
    Online Resource
    The Electrochemical Society ; 2019
    In:  ECS Meeting Abstracts Vol. MA2019-02, No. 6 ( 2019-09-01), p. 485-485
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-02, No. 6 ( 2019-09-01), p. 485-485
    Abstract: The ability to store large amounts of electrical energy is of increasing importance with the growing fraction of electricity generation from intermittent renewable sources such as wind and solar. Flow batteries show promise because the designer can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all electro-active species in fluids. Wide-scale utilization of flow batteries is limited by the abundance and cost of these materials, particularly those utilizing redox-active metals such as vanadium or precious metal electrocatalysts. We have developed high performance flow batteries based on the aqueous redox behavior of small organic and organometallic molecules, e.g. [1-10]. These redox active materials can be inexpensive and exhibit rapid redox kinetics and long lifetimes, although short lifetimes are more common [7] . We have developed new protocols for measuring capacity fade rates and have discovered that the capacity fade rate is typically determined by the molecular calendar life, which can depend on state of charge, but is independent of the number of charge-discharge cycles imposed [7]. We will report the performance of the few chemistries with long enough calendar life, or the potential for acquiring long enough calendar life [9] , for practical application in stationary storage. [1] B. Huskinson, M.P. Marshak, C. Suh, S. Er, M.R. Gerhardt, C.J. Galvin, X. Chen, A. Aspuru-Guzik, R.G. Gordon and M.J. Aziz, "A metal-free organic-inorganic aqueous flow battery", Nature 505 , 195 (2014), http://dx.doi.org/10.1038/nature12909 [2] K. Lin, Q. Chen, M.R. Gerhardt, L. Tong, S.B. Kim, L. Eisenach, A.W. Valle, D. Hardee, R.G. Gordon, M.J. Aziz and M.P. Marshak, "Alkaline Quinone Flow Battery", Science 349 , 1529 (2015), http://dx.doi.org/10.1126/science.aab3033 [3] K. Lin, R. Gómez-Bombarelli, E.S. Beh, L. Tong, Q. Chen, A.W. Valle, A. Aspuru-Guzik, M.J. Aziz, and R.G. Gordon, "A redox flow battery with an alloxazine-based organic electrolyte", Nature Energy 1 , 16102 (2016). http://dx.doi.org/10.1038/nenergy.2016.102 [4] E.S. Beh, D. De Porcellinis, R.L. Gracia, K.T. Xia, R.G. Gordon and M.J. Aziz, "A Neutral pH Aqueous Organic/Organometallic Redox Flow Battery with Extremely High Capacity Retention", ACS Energy Letters 2 , 639 (2017). http://dx.doi.org/10.1021/acsenergylett.7b00019 [5] Z. Yang, L. Tong, D.P. Tabor, E.S. Beh, M.-A. Goulet, D. De Porcellinis, A. Aspuru-Guzik, R.G. Gordon, and M.J. Aziz, "Alkaline benzoquinone aqueous flow battery for large-scale storage of electrical energy” Advanced Energy Materials 2017 , 1702056 (2017). http://dx.doi.org/10.1002/aenm.201702056 [6] D.G. Kwabi, K. Lin, Y. Ji, E.F. Kerr, M.-A. Goulet, D. DePorcellinis, D.P. Tabor, D.A. Pollack, A. Aspuru-Guzik, R.G. Gordon, and M.J. Aziz, “Alkaline Quinone Flow Battery with Long Lifetime at pH 12” Joule 2 , 1907 (2018). https://doi.org/10.1016/j.joule.2018.07.005 [7] M.-A. Goulet & M.J. Aziz, “Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods”, J. Electrochem. Soc. 165 , A1466 (2018). http://dx.doi.org/10.1149/2.0891807jes [8] Y. Ji, M.-A. Goulet, D.A. Pollack, D.G. Kwabi, S. Jin, D. DePorcellinis, E.F. Kerr, R.G. Gordon, and M.J. Aziz, “A phosphonate-functionalized quinone redox flow battery at near-neutral pH with record capacity retention rate” Advanced Energy Materials 2019 1900039; https://doi.org/10.1002/aenm.201900039 [9] M.-A. Goulet, L. Tong, D.A. Pollack, D.P. Tabor, E.E. Kwan, A. Aspuru-Guzik, R.G. Gordon, and M.J. Aziz, “Extending the lifetime of organic flow batteries via redox state management” Journal of the American Chemical Society 141 , in press (2019); https://doi.org/10.1021/jacs.8b13295 [10] http://aziz.seas.harvard.edu/electrochemistry
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
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  • 5
    Online Resource
    Online Resource
    The Electrochemical Society ; 2022
    In:  ECS Meeting Abstracts Vol. MA2022-01, No. 3 ( 2022-07-07), p. 486-486
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2022-01, No. 3 ( 2022-07-07), p. 486-486
    Abstract: Organic and metalorganic reactants have become promising for long-lifetime flow batteries. Synthetic chemistry unlocks a wide design space to tailor reactant redox potential, solubility, chemical and electrochemical stability, redox kinetics, and transport properties. Minimizing the crossover of reactants through the membrane or separator is one crucial design goal. To that end, this work contributes a systematic evaluation of size- and charge-based effects on small molecule permeability through Nafion. These results inform the design of flow battery electrolytes that improve the transport selectivity of ion exchange membranes. Some recent flow battery designs have included crossover suppression strategies based on size and charge of reactants. One option is to leverage size-exclusion, for example by tethering redox-active moieties to polymer backbones, 1,2 or by oligomerizing redox-active monomers. 3-5 A charge-based strategy has been employed to decrease viologen crossover: sulfonate 6 or phosphonate 7 solubilizing groups were attached to the redox active core and paired with a cation exchange membrane, reducing crossover compared to previous iterations of this chemistry. Crossover rates of some organic-based flow battery molecules have been estimated to be very low, but other considerations must be balanced for designing viable battery technology. For example, electrolyte cost and solubility may be in direct tension with a crossover suppression strategy based on increasing redox mediator size. 8 Untangling the effects of different membrane-molecule selectivity mechanisms is a valuable step on the path to advancing redox active molecule design. This work evaluates a set of quinones in which size is varied by the number of aromatic rings ( e.g. hydroquinone, anthraquinone) and charge number is varied almost independently through sulfonation. Each sulfonate moiety contributes a -1 charge, increasing the magnitude of the molecule charge number with the same sign as the fixed charges in Nafion. Effective size of solvated species is accessed through rotating disk electrode voltammetry: Stokes radii are calculated from measured diffusion coefficients. We found over an order of magnitude permeability reduction per sulfonate, emphasizing the importance of charge-based exclusion for ion exchange membranes. In comparison, size-exclusion effects are less impactful. For example, the Stokes radius of anthraquinone 2,6-disulfonate (AQDS) is twice that of hydroquinone 2,5-disulfonate but their permeabilities fall within the same order of magnitude. 1. T. Hagemann, J. Winsberg, M. Grube, I. Nischang, T. Janoschka, N. Martin, M. D. Hager, and U. S. Schubert, Journal of Power Sources, 378 , 546 (2018). 2. T. Janoschka, N. Martin, U. Martin, C. Friebe, S. Morgenstern, H. Hiller, M. D. Hager, and U. S. Schubert, Nature , 527 , 78 (2015). 3. M. J. Baran, M. N. Braten, E. C. Montoto, Z. T. Gossage, L. Ma, E. Chenard, J. S. Moore, J. Rodrıguez-Lopez, and B. A. Helms, Chemistry of Materials , 30 , 3861 (2018). 4. K. H. Hendriks, S. G. Robinson, M. N. Braten, C. S. Sevov, B. A. Helms, M. S. Sigman, S. D. Minteer, and M. S. Sanford, ACS Central Science , 4 , 189 (2018). 5. S. E. Doris, A. L. Ward, A. Baskin, P. D. Frischmann, N. Gavvalapalli, E. Chenard, C. S. Sevov, D. Prendergast, J. S. Moore, and B. A. Helms, Angewandte Chemie, 129 , 1617 (2017). 6. C. Debruler, B. Hu, J. Moss, J. Luo, and T. L. Liu, ACS Energy Letters , 3 , 663, (2018). 7. S. Jin, E. M. Fell, L. Vina-Lopez, Y. Jing, P. W. Michalak, R. G. Gordon, and M. J. Aziz, Advanced Energy Materials , 10 , (2020). 8. M. L. Perry, J. D. Saraidaridis, and R. M. Darling, Current Opinion in Electrochemistry, 21 , 311 (2020).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2022
    detail.hit.zdb_id: 2438749-6
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