Computational and experimental investigation of the effect of cation structure on the solubility of anionic flow battery active-materials

Visayas, Benjoe Rey B.; Pahari, Shyam K.; Gokoglan, Tugba Ceren; Golen, James A.; Ağar, Ertan; Cappillino, Patrick; Mayes, Maricris L.

doi:10.1039/d1sc04990a

Cited by 10 publications

(11 citation statements)

References 54 publications

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“…The hydrogens in CH 3 CN, although classied as aprotic, possess a slight acidity (Abraham's hydrogen bond acidity, a MeCN = 0.07) 62 and the addition of water (Abraham's hydrogen bond acidity, a water = 0.82) 63 supplements the solvent mixture with more acidic protons than CH 3 CN alone. 1,64,65 The possible promoting effect of water in alkane oxidation by assisting proton transfer steps has been rationalized by DFT calculations. 66,67 The oxidation of cyclohexane catalyzed by various metal complexes is expected to follow a radical mechanism (Scheme 3).…”

Section: Cyclohexane Oxidation Catalysis Under Microwave Irradiationmentioning

confidence: 99%

Triazaphosphaadamantane-functionalized terpyridine metal complexes: cyclohexane oxidation in homogeneous and carbon-supported catalysis

et al. 2023

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Section: Cyclohexane Oxidation Catalysis Under Microwave Irradiationmentioning

confidence: 99%

Triazaphosphaadamantane-functionalized terpyridine metal complexes: cyclohexane oxidation in homogeneous and carbon-supported catalysis

et al. 2023

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“…[6] The thermodynamic solubility of active materials in electrolytes is determined by the lattice and solvation energies. [7] Molecular engineering of organic molecules by introducing hydrophilic groups is one of the most common strategies to promote the solubility in water. [8,9] The traditional approach to formulating redox electrolytes, however, provides little control over the solution structure, and thus is incapable of escaping from the thermodynamic constraint.…”

Section: Introductionmentioning

confidence: 99%

Grafting and Solubilization of Redox‐Active Organic Materials for Aqueous Redox Flow Batteries

Chen¹,

Zhang

Chang

et al. 2023

ChemSusChem

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This study concerns the development of sustainable design strategies of aqueous electrolytes for redox flow batteries using redox-active organic materials. A green spontaneous grafting reaction occurs between a redox-active organic radical and an electrochemically activated structural modifier at room temperature through a simple mixing step. Then, a physical mixing method is used to formulate a structured aqueous electrolyte and enables aqueous solubilization of the organic solute from below 0.5 to 1.5 m beyond the conventional dissolution limit. The as-obtained concentrated mixture can be readily used as catholyte for a redox flow battery. A record high discharge cell voltage (1.6 V onset output voltage) in aqueous non-hybrid flow cell is attained by using the studied electrolytes.

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“…Despite the many advantages NRFBs may offer, none of these chemistries has yet penetrated the energy storage market. A great deal of experimental, ,, theoretical, − or combined experimental–theoretical , works have been done in an effort to increase the solubility of active materials. The experimental methods include functionalization of redox active cores, ionic modification, counterion tuning, , solvent ratio manipulation, and utilizing eutectic mixtures .…”

Section: Introductionmentioning

confidence: 99%

Toward High-Performance Nonaqueous Redox Flow Batteries through Electrolyte Design

Pahari

Gokoglan

Chaurasia

et al. 2023

ACS Appl. Energy Mater.

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Redox flow batteries (RFBs) have emerged as a promising solution for large-scale stationary energy storage. However, nonaqueous flow batteries, despite having promising potential, are lagging behind aqueous flow batteries due to the lack of suitable redox pairs that can deliver high energy density and long cycle life. In this study, we implemented a counterion modification strategy to greatly enhance the solubility of both catholyte and anolyte active materials. Specifically, we increased the solubility of anthraquinone-2-sulfonic acid sodium salt (AQS) by three orders of magnitude in acetonitrile by replacing a sodium countercation with tetra-nbutylammonium. We present the first report of the flow cell cycling of all anionic active materials with a tetra-n-butyl countercation in supporting-salt-free conditions. We investigated the electrochemical behavior of each individual active material in a symmetric flow cell and then paired the AQS anolyte with the bio-inspired catholyte, tetra-n-butylammonium vanadium-bis-hydroxyiminodiacetate (TBA 2 VBH), in a full cell. The significant crossover observed in a full cell was mitigated by using a compositionally symmetric, mixed electrolyte as both the catholyte and anolyte. Additionally, because AQS and VBH coexist stably in the mixed electrolyte, even at high concentrations, we demonstrate that the cell capacity can be fully restored by rebalancing the electrolyte leading to long cycle life. This strategy, which has been employed in aqueous, acidic, all-vanadium flow battery systems, could be a promising pathway toward robust, highperformance nonaqueous flow batteries.

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Computational and experimental investigation of the effect of cation structure on the solubility of anionic flow battery active-materials

Abstract: Active-material solubility is critical in determining NRFB energy density, yet a predictive model accounting for solid-state cohesion energy has remained elusive. Herein we present such, based on an empirically calibrated computational framework.

Cited by 10 publications

References 54 publications

Triazaphosphaadamantane-functionalized terpyridine metal complexes: cyclohexane oxidation in homogeneous and carbon-supported catalysis

Triazaphosphaadamantane-functionalized terpyridine metal complexes: cyclohexane oxidation in homogeneous and carbon-supported catalysis

Grafting and Solubilization of Redox‐Active Organic Materials for Aqueous Redox Flow Batteries

Toward High-Performance Nonaqueous Redox Flow Batteries through Electrolyte Design

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