Understanding and Mitigating Capacity Fade in Aqueous Organic Redox Flow Batteries

Murali, Advaith; Nirmalchandar, Archith; Krishnamoorthy, Sankarganesh; Hoober-Burkhardt, Lena; Yang, Bo; Soloveichik, Grigorii L.; Prakash, G. K. Surya; Narayanan, S. R.

doi:10.1149/2.0161807jes

Cited by 67 publications

(67 citation statements)

References 32 publications

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“…The formation of these carbocations was recently reported as a key step in the capacity fade mechanism for DHDMBS. 25 Another potential strategy could be to modulate the pKas of the redox-active sites of the reduced form of these couples. This would lead to a "flattening out" of the potential on the Pourbaix diagram at lower pH and could lead to otherwise unpromising molecules at pH = 0 becoming viable at higher values of pH.…”

Section: Resultsmentioning

confidence: 99%

Theoretical and Experimental Investigation of the Stability Limits of Quinones in Aqueous Media: Implications for Organic Aqueous Redox Flow Batteries

Tabor¹,

Gómez‐Bombarelli²,

Tong³

et al. 2018

Preprint

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<div> <div> <p>Quinone-hydroquinone pairs have been proposed as biologically-inspired, low-cost redox couples for organic electrolytes for electrical energy storage, particularly in aqueous redox flow batteries. In their oxidized form, quinones are electrophiles that can react with the nucleophilic water solvent resulting in loss of active electrolyte. Here we study two mechanisms of nucleophilic addition of water, one reversible and one irreversible, that limit quinone performance in practical flow batteries. Using a combination of density functional theory and semi-empirical calculations, we have quantified the source of the instability of quinones in water, and explored the relationships between chemical structure, electrochemical reduction potential, and decomposition or instability mechanisms. By combining these computational estimates with the experimental study of the aqueous stability of alizarin-derived quinones, quantitative thresholds for chemical stability of oxidized quinones were established. Finally, ∼140,000 prospective quinone pairs (over 1,000,000 calculations including decomposition products) were analyzed in a virtual screening using the learned design principles. Our conclusions suggest that numerous low reduction potential molecules are stable with respect to nucleophilic addition, but promising high reduction potential molecules are much rarer. This latter fact suggests the existence of a stability cliff for this family of quinone-based organic molecules, which challenges the development of all-quinone aqueous redox flow batteries.<br></p> </div> </div>

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Section: Resultsmentioning

confidence: 99%

Theoretical and Experimental Investigation of the Stability Limits of Quinones in Aqueous Media: Implications for Organic Aqueous Redox Flow Batteries

Tabor¹,

Gómez‐Bombarelli²,

Tong³

et al. 2018

Preprint

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“…Although it is promising to develop electrolytes with high effective concentration, many studies show deteriorated performance with high organic concentration . Knowledge gaps exist in the fundamental understanding of capacity fade mechanisms . Analytical methods to examine the reaction mechanisms and to characterize the reversibility and durability of organic molecules should be developed for optimizing performance and broadening applicability for industrial use.…”

Section: Conclusion and Perspectivementioning

confidence: 99%

Toward High‐Voltage, Energy‐Dense, and Durable Aqueous Organic Redox Flow Batteries: Role of the Supporting Electrolytes

Chen

2018

ChemElectroChem

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Sustainable energy supply from renewable sources requires highly efficient and economically competitive energy-storage technologies. With flexible design, high energy-storage efficiency, and long-term cyclability, redox flow batteries are superior candidates for peak shaving and load leveling for smart grids in the energy generation, storage and distribution networks. With natural abundance, structural diversity and tunability, redox-active organic species as valuable alternatives to the traditional inorganic-based materials are promising to tackle the resource and performance limitations. To design aqueous organic redox flow batteries toward energy-dense, high-rate performance and durability, in this Review, strategies to maximize the cell voltage, effective concentration of organic species, and operating current density are discussed. Besides the inherent nature of the organic molecules, suitable solvents and supporting ions can affect their solvation behavior and promote their chemical stability.[a] Dr.A patent concerning supporting electrolyte for organic materials has been filed by KIST Europe and CMBlu Projekt AG (PCT/ EP2018/056087) that names R.C. as an inventor.

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“…The chemical structure of Tiron is then transformed into desirable 2,4,5,6-tetrahydroxybenzene-1,3-disulfonic acid (TironA) by Michael addition reaction occurring during the first cycle of QRFB. [24][25][26][27][28] Once TironA is formed, a desirable redox reaction occurs and the stable and reproducible charge and discharge steps of QRFB are continued from the second cycle. 24 In spite of that, the electron transfer rate of TironA is still low, and the performance of QRFB using TironA, especially the voltage and energy efficiencies (VE and EE).…”

Section: Introductionmentioning

confidence: 99%

The effect of plasma treated carbon felt on the performance of aqueous quinone‐based redox flow batteries

Permatasari

Shin

Lee

et al. 2021

Intl J of Energy Research

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4,5-dihydroxybenzene-1,3-disulfonic acid (Tiron) and anthraquinone-2,-7-disulfonic acid (AQDS) are interesting redox couples for aqueous quinonebased redox flow batteries (QRFBs) because of their high solubility and good reaction reversibility in acidic condition. Tiron is rate-determining material due to its slow reaction kinetics. To improve that, Tiron is transformed into 2,4,5,6-tetrahydroxybenzene-1,3-disulfonic acid (TironA), which is effectively formed during the first cycle of QRFB. Once TironA is formed, a desirable two-electron redox reaction with stable and reproducible charge and discharge step of QRFB occurs, although the electron transfer of TironA is still lower than that of AQDS. To further facilitate that of TironA, oxygen (O 2 ) and nitrogen (N 2 ) plasma-treated carbon felt (CF) electrodes are suggested. Oxygen functional groups formed onto CF by O 2 plasma become the active sites for redox reaction of TironA. As the amount of oxygen functional groups formed increases, the redox reactivity of TironA is enhanced. In contrast, when N 2 plasma is used, pyrrolic N and quaternary N are mainly formed. With the formation, (i) hydrogen atoms within pyrrolic N act as proton donor and interact with oxygen groups of TironA and (ii) nitrogen cations within quaternary N interact with the negatively charged atoms of TironA by electrostatic interaction. Thus, both reaction kinetic of TironA and performance of QRFB increase.Regarding the performance of QRFB using N 2 plasma-treated CF, its energy efficiency (EE), discharging capacity, and state of charge are 62%, 17.3 AhrÁL À1 and 64.5% for 50 cycle, which correspond to excellent achievements.

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Understanding and Mitigating Capacity Fade in Aqueous Organic Redox Flow Batteries

Cited by 67 publications

References 32 publications

Theoretical and Experimental Investigation of the Stability Limits of Quinones in Aqueous Media: Implications for Organic Aqueous Redox Flow Batteries

Theoretical and Experimental Investigation of the Stability Limits of Quinones in Aqueous Media: Implications for Organic Aqueous Redox Flow Batteries

Toward High‐Voltage, Energy‐Dense, and Durable Aqueous Organic Redox Flow Batteries: Role of the Supporting Electrolytes

The effect of plasma treated carbon felt on the performance of aqueous quinone‐based redox flow batteries

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