Desymmetrized hexasubstituted [3]radialene anions as aqueous organic catholytes for redox flow batteries

Turner, Nicholas; Freeman, Matthew B.; Pratt, Harry D.; Crockett, Austin E.; Jones, Daniel S.; Anstey, Mitchell R.; Anderson, Travis M.; Bejger, Christopher

doi:10.1039/c9cc08547e

Cited by 15 publications

(18 citation statements)

References 34 publications

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“…An AOFB consists of organic compounds with high redox potential for the positive side (catholyte) and organic counterparts with low redox potential for the negative side (anolyte). Although great success has been achieved for the anolyte, with an extremely low capacity fade rate of ≤0.02 % per day demonstrated, [3b,4] the few options for the organic catholyte include functionalized benzoquinones, [5] radialene dianions, [6] ferrocene [7] and 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) derivatives [8] . Benzoquinones have been operated under highly acidic solutions and exhibit poor stability due to side reactions [9] .…”

Section: Introductionmentioning

confidence: 99%

“…Benzoquinones have been operated under highly acidic solutions and exhibit poor stability due to side reactions [9] . Radialene dianions are chemically unstable and poorly soluble in water [6] . Ferrocene and TEMPO derivatives are the best‐performing organic catholyte options, but their performance to date does not merit commercialization [3b] …”

Section: Introductionmentioning

confidence: 99%

“…[9] Radialene dianions are chemically unstable and poorly soluble in water. [6] Ferrocene and TEMPO derivatives are the best-performing organic catholyte options, but their performance to date does not merit commercialization. [3b] A challenging task is the hydrophilic functionalization of ferrocene and TEMPO derivatives for enhanced water solubility, as most of them are barely soluble in water.…”

Section: Introductionmentioning

confidence: 99%

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Functioning Water‐Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host–Guest Inclusion

Qing

et al. 2020

ChemSusChem

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Ferrocene (Fc) is one of the very limited organic catholyte options for aqueous organic flow batteries (AOFBs), a potential electrochemical energy storage solution to the intermittency of renewable electricity. Commercially available Fc derivatives are barely soluble in water, while existing methods for making water-soluble Fc derivatives by appending hydrophilic or charged moieties are tedious and time-consuming, with low yields. Here, a strategy was developed based on host-guest inclusion to acquire water-soluble Fc-based catholytes by simply mixing Fc derivatives with β-cyclodextrins (β-CDs) in water. Factors determining the stability and the electrochemical behavior of the inclusion complexes were identified. When adopted in a neutral pH AOFB, the origin of capacity loss was identified to be a chemical degradation caused by the nucleophilic attack on the center Fe III atom of the oxidized Fc derivatives. By limiting the state of charge, a low capacity fade rate of 0.0073 % h À 1 (or 0.0020 % per cycle) was achieved. The proposed strategy may be extended to other families of electrochemically active water-insoluble organic compounds, bringing more electrolyte options for practical AOFB applications.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Functioning Water‐Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host–Guest Inclusion

Qing

et al. 2020

ChemSusChem

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“…Interest in developing water-stable NRFB analytes remains high for ease of handling and because the presence of water lowers flammability. 12,25 In addition, Al is the most abundant metal in the earth's crust (8%), 26 and its ability to enhance the redox properties of organic analytes adds further interest for large scale application.…”

mentioning

confidence: 99%

“…The advance presented herein lies in our use of Al(III) as the supporting metal ion which does not enter into the redox chemistry and thus maintains stability during long periods of charge cycling even when solvents contain trace water (Scheme ). Interest in developing water-stable NRFB analytes remains high for ease of handling and because the presence of water lowers flammability. , In addition, Al is the most abundant metal in the earth’s crust (8%), and its ability to enhance the redox properties of organic analytes adds further interest for large scale application.…”

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confidence: 99%

A Stable Organo-Aluminum Analyte Enables Multielectron Storage for a Nonaqueous Redox Flow Battery

Arnold

Dougherty

Carr

et al. 2020

J. Phys. Chem. Lett.

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Redox flow batteries (RFBs) operate by storing electrons on soluble molecular anolytes and catholytes, and large increases in the energy density of RFBs could be achieved if multiple electrons could be stored in each molecular analyte. Here, we report an organoaluminum analyte, [(I2P–)2Al]+, in which four electrons can be stored on organic ligands, and for which charging and discharging cycles performed in a symmetric nonaqueous RFB configuration remain stable for over 100 cycles at 70% state of charge and 97% Coulombic efficiency (I2P is a bis(imino)pyridine ligand). The stability of the analyte is promoted by the kinetic inertness of the anolyte to trace water in solvents and by the redox inertness of the Al(III) ion to the applied current. The solubility of the analyte was optimized by exchanging the counteranion for trifluoromethanesulfonate (triflate), and the cell was further optimized using graphite rods as electrodes which, in comparison with glassy carbon and reticulated vitreous carbon, eliminated deposition of analyte on the electrode. Proof-of-principle experiments performed with an asymmetric NRFB configuration further demonstrate that up to four electrons can be stored in the cell with no degradation of the analyte over multiple cycles that show 96% Coulombic efficiency.

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Solution‐Doped Donor–Acceptor Copolymers Based on Diketopyrrolopyrrole and 3, 3′‐Bis (2‐(2‐(2‐Methoxyethoxy) Ethoxy) ethoxy)‐2, 2′‐Bithiophene Exhibiting Outstanding Thermoelectric Power Factors with p‐Dopants

Mukhopadhyaya,

Wagner,

Lee

et al. 2023

Adv Funct Materials

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The design of polymeric semiconductors exhibiting high electrical conductivity (σ) and thermoelectric power factor (PF) will be vital for flexible large‐area electronics. In this work, four polymers based on diketopyrrolopyrrole (DPP), 2,3‐dihydrothieno[3,4‐b][1,4]dioxine (EDOT), thieno[3,2‐b]thiophene (TT), and 3, 3′‐bis (2‐(2‐(2‐methoxyethoxy) ethoxy) ethoxy)‐2, 2′‐bithiophene (MEET) are investigated as side‐chains, with the MEET polymers newly synthesized for this study. These polymers are systematically doped with tetrafluorotetracyanoquinodimethane ( F4TCNQ), CF3SO3H, and the synthesized dopant Cp(CN)3‐(COOMe)3, differing in geometry and electron affinity. The DPP‐EDOT‐based polymer containing MEET as side‐chains exhibits the highest conductivity (σ) ≈700 S cm−1 in this series with the acidic dopant (CF3SO3H). This polymer also shows the lowest oxidation potential by cyclic voltammetry (CV), the strongest intermolecular interactions evidenced by differential scanning calorimetry (DSC), and has the most oxygen‐based functionality for possible hydrogen bonding and ionic screening. Other polymers exhibit high σ ≈300–500 S cm−1 and power factor up to 300 µW m−1 K−2. The mechanism of conductivity is predominantly electronic, as validated by time‐dependent conductance studies and transient thermo voltage monitoring over time, including for those doped with the acid. These materials maintain significant thermal stability and air stability over ≈6 weeks. Density functional theory calculations reveal molecular geometries and inform about frontier energy levels. Raman spectroscopy, in conjunction with scanning electron microscopy (SEM‐EDS) and x‐ray diffraction, provides insight into the solid‐state microstructure and degree of phase separation of the doped polymer films. Infrared spectroscopy enables this study to further quantify the degree of charge transfer from polymer to dopant.

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Desymmetrized hexasubstituted [3]radialene anions as aqueous organic catholytes for redox flow batteries

Abstract: Hexasubstituted [3]radialenes can be synthetically tuned to function as catholyte materials for neutral pH aqueous organic redox flow batteries.

Cited by 15 publications

References 34 publications

Functioning Water‐Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host–Guest Inclusion

Functioning Water‐Insoluble Ferrocenes for Aqueous Organic Flow Battery via Host–Guest Inclusion

A Stable Organo-Aluminum Analyte Enables Multielectron Storage for a Nonaqueous Redox Flow Battery

Solution‐Doped Donor–Acceptor Copolymers Based on Diketopyrrolopyrrole and 3, 3′‐Bis (2‐(2‐(2‐Methoxyethoxy) Ethoxy) ethoxy)‐2, 2′‐Bithiophene Exhibiting Outstanding Thermoelectric Power Factors with p‐Dopants

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