Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries

VanGelder, Lauren E.; Kosswattaarachchi, Anjula M.; Forrestel, Patrick L.; Cook, Timothy R.; Matson, Ellen M.

doi:10.1039/c7sc05295b

Cited by 139 publications

(187 citation statements)

References 62 publications

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“…As such, we measured the solubility of 1‐L a in acetonitrile with 0.1 m [NBu 4 ][PF 6 ], thus mimicking the working conditions of a NRFB cell (Figure S4). We found the solubility of 1‐L a to be 0.214 m , a nominal increase over its homoleptic congener, 1 (0.203 m ) . Previous work has demonstrated that decreasing the symmetry of charge carrier complexes disfavors crystal packing, increasing the solubility of these compounds .…”

Section: Resultssupporting

confidence: 66%

“… Select examples of previously reported nonaqueous charge carriers composed of one or more transition metals. Specific attention has been called to examples that highlight synthetic strategies aimed to improve the stability and solubility of molecular redox‐active species …”

Section: Introductionmentioning

confidence: 94%

“…Recently, our research group reported polyoxovanadate–alkoxide (POV–alkoxide) clusters as a promising new class of charge carriers for NRFBs . In our initial work, we focused on the previously reported mixed‐valent, Lindqvist structures, [V 6 O 7 (OR) 12 ] (R=CH 3 , C 2 H 5 ) (Figure ) . Although we were able to demonstrate that the ethoxide derivative of the hexavanadate cluster was capable of serving as a two‐electron charge carrier ( n= 2) in a symmetric schematic, the poor solubility of this assembly in acetonitrile (0.05 m ) resulted in a low theoretical energy density.…”

Section: Introductionmentioning

confidence: 99%

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Organic Functionalization of Polyoxovanadate–Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries

et al. 2018

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The success of nonaqueous redox flow battery technology requires synthetic advances in charge carrier design to increase compatibility with organic solvents. Herein, previous discoveries related to the development of multimetallic charge carriers are built upon with the high‐yielding syntheses of ether‐ functionalized polyoxovanadate–alkoxide clusters, [V6O7(OR)9(OCH2)3CR′] (R=CH3, C2H5; R′=CH3, CH2OCH3, CH2OC2H4OCH3). Like their homoleptic congeners [V6O7(OR)12] (R=CH3, C2H5), these clusters exhibit four redox events, spanning nearly a two‐volt window, and demonstrate rapid electron‐transfer kinetics. The ethoxide derivatives can reversibly cycle two electrons at each electrode in symmetric charging schematics, demonstrating long‐term solution stability. Furthermore, ether functionalization yields a twelvefold increase in solubility, a factor which directly dictates the energy density of a redox flow battery.

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Section: Resultssupporting

confidence: 66%

Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Organic Functionalization of Polyoxovanadate–Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries

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“…Non‐innocent ligands have been prominently targeted of late, with examinations of bipyridine complexes, modified versions, and three‐coordinate hybrids . Recently, polyoxometalate complexes have been revised for nonaqueous systems, exhibiting excellent reversibility albeit with a relatively small potential …”

Section: Figurementioning

confidence: 99%

“…[13] Recently,p olyoxometalate complexes have been revisedf or nonaqueoussystems, exhibiting excellent reversibility albeit with ar elativelys mall potential. [14] Cost is the ultimate driver for RFB implementation, [15] and to meet those targets many researchers are focusingo nt he redox carriers that show very high solubilities (> 2.5 m), carry > 2electrons per molecule, and produce a > 3Vcell potential. To meet these goals, we were intrigued by the ability of aN icyclam complex to generate ac ell potential of approximately 2.5 Va nd operate in both half-reactions of the cell.…”

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Linked Picolinamide Nickel Complexes as Redox Carriers for Nonaqueous Flow Batteries

et al. 2019

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The use of nickel complexes utilizing non-innocent ligands based on picolinamide to functiona sr edox carriers in flow batteries was explored. The picolinamidem oiety was linked together with ÀCH 2 CH 2 À (bpen), ÀCH 2 CH 2 CH 2 À (bppn), and ÀC 6 H 4 À (bpb) moieties, resulting in two, three, and four quasireversible waves, respectively,f or the nickel complexes and > 3V differenceb etween the outermost positivea nd negative waves. Ther edox events were theoretically modelled for each complex, showinge xcellent agreement (< 0.3 Vd ifference)b etween the experimental and modelled potentials. Bulk cycling of the most soluble complex, Ni(bppn), indicated only one of the three waves was reversible. Therefore, Ni(bppn) has the ability to act as an egative charge redox carrier in flow cells.Although lithium ion batteries tend to dominate the headlines, grid-scale energy storagew ill be served by av ariety of technologies depending on the time period of service. [1] For several decades, one technology attractive for > 4h of discharge is the redox flow battery (RFB, Figure 1). In contrastt os econdary batteries, in which the energy is stored within stationarye lectrodes, RFBs store and release energy from ar edox reaction between soluble chemical species, called redox carriers. At ypical non-hybrid RFB design has two storage tanks for the redox carriers that can be scaled independently of the cell, thereby imparting greater flexibility than as econdary battery,i nw hich power and energy are coupled( Figure1). Aqueousv anadium RFBs are the most developed technology availabley et suffer from the high cost of precursors (vanadium) and low stored energy density.D emand for improvements in energy storage has seen RFB research explode with significant advances: [2] greatly improved vanadium RFBc apacities, [3] identification of

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Redox‐Active Inorganic Materials for Redox Flow Batteries

Luo

Debruler

et al. 2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Continuous growth in utilization of renewable but intermittent energy such as solar and wind will accelerate the demand for grid‐scale energy storage systems. Redox flow batteries (RFBs) have been intensively studied for large‐scale energy storage (MW/MWh), which is particularly attractive when integrated with renewable energy sources. In past decades, extensive efforts have been made to improve electrochemical performance of the RFBs by exploring various active materials, from inorganic redox‐active materials to organic redox‐active molecules. Compared to burgeoning organic RFBs, inorganic RFBs have received extensive research and development in the last several decades. A great deal of efforts has been exerted to commercialize several inorganic RFB systems such as all‐vanadium RFBs and zinc–bromine RFBs. In this article, inorganic redox‐active materials (e.g., metal salts, halides, polysulfides, polyoxometalate (POM), etc.) applied in RFBs are reviewed with a primary focus on their most recent technological advances in aqueous inorganic RFBs. The advantages and limitations of different inorganic RFBs are discussed. Further technological challenges and perspective on inorganic RFBs are also highlighted.

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Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries

Abstract: Installation of bridging alkoxide ligands leads to improvements to solubility, stability and redox profile of POM clusters!

Cited by 139 publications

References 62 publications

Organic Functionalization of Polyoxovanadate–Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries

Organic Functionalization of Polyoxovanadate–Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries

Linked Picolinamide Nickel Complexes as Redox Carriers for Nonaqueous Flow Batteries

Redox‐Active Inorganic Materials for Redox Flow Batteries

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