A nonaqueous organic redox flow battery using multi-electron quinone molecules

Pahlevaninezhad, Maedeh; Leung, Puiki; Velasco, Pablo Quijano; Pahlevani, Majid; Walsh, Frank C.; Roberts, Edward P.L.; León, Carlos Ponce de

doi:10.1016/j.jpowsour.2021.229942

Cited by 43 publications

(25 citation statements)

References 49 publications

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“…71 It has a somewhat high viscosity (η = 1.64 mPa s); however, solvents of higher viscosity, such as DMSO (η = 1.99 mPa s) have been employed successfully in flow cells. 8,72,73 Furthermore, the polarity of MB (E T (30) = 38.7) is comparable to that of o-DCB (E T (30) = 38.0). 74,75 Upon establishing conditions to foster high stability of the active material, we then assessed the kinetics of electron transfer for PZtBuTH (9), PQtBuTH (8), and QXtBuTH (10).…”

Section: ■ Results and Discussionmentioning

confidence: 86%

Thianthrene-Based Bipolar Redox-Active Molecules Toward Symmetric All-Organic Batteries

Etkind

Lopez

Zhu

et al. 2022

ACS Sustainable Chem. Eng.

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Bipolar redox activity is generally obtained using a single moiety that can be both oxidized and reduced or by tethering two distinct redox active molecules, together with a covalent linker. Herein, we demonstrate an alternative approach using the SNAr and SNAr-type reactions of benzene-1,2-dithiols and electron-deficient aromatic halides or halogenated quinones to prepare a family of compact, thianthrene-based bifunctional molecules. The potential of these molecules as electrolytes for redox flow batteries was assessed in static cells as a proof of concept. Cycling in a static cell demonstrated that the thianthrene-quinone, PQtBuTH (8), is highly stable, compared to other symmetric organic active materials, with 44% capacity retention over 450 cycles (16.7 days), and an initial energy density of 1.3Wh/L at a concentration of 0.1 M. Redox flow batteries represent a promising grid-scale energy storage technology, and the development of new symmetric electrolyte systems in organic solvents can potentially mitigate issues associated with membrane crossover and provide high cell voltages.

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Section: ■ Results and Discussionmentioning

confidence: 86%

Thianthrene-Based Bipolar Redox-Active Molecules Toward Symmetric All-Organic Batteries

Etkind

Lopez

Zhu

et al. 2022

ACS Sustainable Chem. Eng.

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show abstract

“…(2021) [24] DB-1 2.60 J. Power Sources (2021) [30] P5Q 2.60 JACS (2014) [49] CA (1 electron) suggest that understanding the interface between CA and solvent molecules may hold the key information toward designing future high-performance organic active materials. Table 3 compares the discharge voltages of CA measured here with other state-of-the-art organic small molecules that undergo multi-electron redox reactions.…”

Section: Moleculesmentioning

confidence: 99%

“…However, to the best of our knowledge, only a few organic active materials that undergo multi‐electron redox reactions at voltages around 4 V against Li/Li + has been reported to date, [ 21 , 22 ] whose theoretical capacities ( C th ) are relatively small (≈250 mAh g –1 ) since they have large molecular weights and the limited number of redox centers. Examples for high‐capacity organic cathode materials including the π ‐conjugated quinoxaline‐based heteroaromatic molecules (≈2.9 V, C th = ≈514 mAh g –1 ), [ 23 , 24 ] carbonyl‐based organic polymers (≈2.5 V, C th = ≈440 mAh g –1 ), [ 25 , 26 , 27 , 28 , 29 ] tetraaminoanthraquinone (≈3.0 V, C th = ≈400 mAh –1 ), [ 30 ] N,N’–substituted phenazine (≈3.7 V, C th = ≈255 mAh g –1 ), [ 21 ] and dibenzo‐1,4‐dioxin–tetracyanoquinodimethane (≈4.2 V, C th = ≈200 mAh g –1 ), [ 22 ] none of them can simultaneously achieve a high‐voltage discharge > 4 V against Li/Li + and a high capacity > 400 mAh g –1 .…”

Section: Introductionmentioning

confidence: 99%

Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?

et al. 2022

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While organic batteries have attracted great attention due to their high theoretical capacities, high‐voltage organic active materials (> 4 V vs Li/Li + ) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium‐ion battery cathode material in both dimethyl sulfoxide and γ ‐butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA–Li 2 ) has two enolate groups that undergo redox reactions above 4.0 V and a material‐level theoretical energy density of 1949 Wh kg –1 for storing four lithium ions in GBL—exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic‐voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery‐performance tests of CA as lithium‐ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g –1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state‐of‐the‐art organic small molecules, CA promises to be a prime cathode‐material candidate for future high‐energy‐density lithium‐ion organic batteries.

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“…For covalent compounds, on the other hand, the one-electron states are delocalized to a certain degree, with non-negligible contributions from more than one species and a larger deviation from one-electron energies of the free ions and their charge distribution around the nuclei. Although, for redox processes involving covalent compounds, FOS are occasionally used for the rationalization of redox processes, e.g., in organic battery materials during cycling [58], the hybridization between different atomic orbitals is widely acknowledged in literature and the discussion of oxidation and reduction processes is often centered around whole functional groups rather than specific atoms [59][60][61]. For redox reactions involving ionic compounds, on the other hand, the FOS concept has proven itself as a powerful tool, condensing the complexity of electronic (and ionic) structure changes during chemical reactions involving electron transfers into effective properties assigned to individual ionic species.…”

Section: Formal Oxidation State Ansatzmentioning

confidence: 99%

Density-Based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-Anchored Framework: A Perspective

et al. 2021

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Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies, including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are, in certain cases, better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.

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A nonaqueous organic redox flow battery using multi-electron quinone molecules

Cited by 43 publications

References 49 publications

Thianthrene-Based Bipolar Redox-Active Molecules Toward Symmetric All-Organic Batteries

Thianthrene-Based Bipolar Redox-Active Molecules Toward Symmetric All-Organic Batteries

Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?

Density-Based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-Anchored Framework: A Perspective

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