Crossover-free hydroxy-substituted quinone anolyte and potassium ferrocyanide catholyte for aqueous alkaline organic redox flow battery

Mirle, Chinmaya; Medabalmi, Veerababu; Ramanujam, Kothandaraman

doi:10.1016/j.cattod.2020.12.012

Cited by 18 publications

(9 citation statements)

References 22 publications

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“…The recent shift away from fossil fuels and toward alternative energy sources has led to an increased focus on energy storage systems . Redox flow batteries (RFBs) store energy in the form of oxidized and reduced redox couples in physically separated solutions allowing long-term storage and facile scalability. − The most well-developed RFB chemistry consists of vanadium salts in acidic solutions, which limit the cell potential to the electrochemical window of water. − The use of a nonaqueous RFB permits a greater cell potential and greater synthetic control. This has led to RFBs that use organic − and organometallic − electrolytes with high cell potentials, multiple electron transfers per molecule, , or both. , …”

Section: Introductionmentioning

confidence: 99%

Investigation of Iron(III) Tetraphenylporphyrin as a Redox Flow Battery Anolyte: Unexpected Side Reactivity with the Electrolyte

Mitchell

Elgrishi

2023

J. Phys. Chem. C

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Redox flow batteries (RFBs) present an opportunity to bridge the gap between the intermittent availability of green energy sources and the need for on-demand grid level energy storage. While aqueous vanadium-based redox flow batteries have been commercialized, they are limited by the constraints of using water as an electrochemical solvent. Nonaqueous redox flow battery systems can be used to produce high voltage batteries due to the larger electrochemical window in nonaqueous solvents and the ability to tune the redox properties of active materials through functionalization. Iron porphyrins, a class of organometallic macrocycles, have been the subject of many studies for their photocatalytic and electrocatalytic properties in nonaqueous solvents. Often, iron porphyrins can undergo multiple redox events making them interesting candidates for use as anolytes in asymmetrical redox flow batteries or as both catholyte and anolyte in symmetrical redox flow battery systems. Here the electrochemical properties of Fe(III)TPP species relevant to redox flow battery electrolytes are investigated including solubility, electrochemical properties, and charge/discharge cycling. Commonly used support electrolyte salts can have reactivities that are often overlooked beyond their conductivity properties in nonaqueous solvents. Parasitic reactions with the cations of common support electrolytes are highlighted herein, which underscore the careful balance required to fully assess the potential of novel RFB electrolytes.

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Section: Introductionmentioning

confidence: 99%

Investigation of Iron(III) Tetraphenylporphyrin as a Redox Flow Battery Anolyte: Unexpected Side Reactivity with the Electrolyte

Mitchell

Elgrishi

2023

J. Phys. Chem. C

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“…RFB using alkaline bislawsone-based negolyte combined with a ferrocyanide posilyte provides comparable OCV (1.05 V) and can be operated at an increased current density of cycling (300 mA/cm 2 ), see Figure 8 [96]. In a recent study, the selected hydroxylated naphthoquinones and anthraquinones were tested as negolytes in an alkaline environment, showing a better performance of the anthraquinonebased molecule, both in terms of the cell voltage and volumetric capacity [97].…”

Section: Naphthoquinone (Two Rings)mentioning

confidence: 99%

Family Tree for Aqueous Organic Redox Couples for Redox Flow Battery Electrolytes: A Conceptual Review

2022

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Redox flow batteries (RFBs) are an increasingly attractive option for renewable energy storage, thus providing flexibility for the supply of electrical energy. In recent years, research in this type of battery storage has been shifted from metal-ion based electrolytes to soluble organic redox-active compounds. Aqueous-based organic electrolytes are considered as more promising electrolytes to achieve “green”, safe, and low-cost energy storage. Many organic compounds and their derivatives have recently been intensively examined for application to redox flow batteries. This work presents an up-to-date overview of the redox organic compound groups tested for application in aqueous RFB. In the initial part, the most relevant requirements for technical electrolytes are described and discussed. The importance of supporting electrolytes selection, the limits for the aqueous system, and potential synthetic strategies for redox molecules are highlighted. The different organic redox couples described in the literature are grouped in a “family tree” for organic redox couples. This article is designed to be an introduction to the field of organic redox flow batteries and aims to provide an overview of current achievements as well as helping synthetic chemists to understand the basic concepts of the technical requirements for next-generation energy storage materials.

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“…This makes a good case for the in-depth study of anthraquinone derivatives as a prospective anode material for practical bulk-scale energy storage applications . This being our motivation, AN was explored as an anolyte in our previous work, but it exhibited limited capacity (1.6 A h L –1 ) due to its poor solubility in aqueous KOH . To improve its solubility, polar functionality (sulfonate) has been introduced to AN to obtain DSAN.…”

Section: Introductionmentioning

confidence: 99%

“…23 This being our motivation, AN was explored as an anolyte in our previous work, but it exhibited limited capacity (1.6 A h L −1 ) due to its poor solubility in aqueous KOH. 24 To improve its solubility, polar functionality (sulfonate) has been introduced to AN to obtain DSAN. K 4 Fe(CN) 6 , a catholyte used in this study, is commonly used as a food additive and does not pose any environmental hazard.…”

Section: Introductionmentioning

confidence: 99%

On Capacity Upgradation and In Situ Capacity Rebalancing in Anthrarufin-Based Alkaline Redox Flow Batteries

Mirle

Ramanujam

2022

ACS Appl. Energy Mater.

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Aqueous organic redox flow batteries (AORFBs) hold great promise in the storage of fluctuating renewable energy output for later use when there is a demand for electricity. Anthrarufin (AN), reported earlier as an anolyte material for the AORFB application, offered limited energy density due to its poor solubility. Here, we present a derivative of AN, 1,5-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2,6-disulfonic acid (DSAN) as an anolyte to improve the energy density of the AORFB. Sulfonic acid functional groups were introduced to hike the solubility of DSAN in an alkaline medium. DSAN is soluble up to 110 mM in 0.4 M KOH and offers a theoretical capacity of 5.9 A h L–1, which is more than twice that of AN. Cyclic voltammetry studies reveal the quasi-reversible nature of DSAN with the redox potential centered at around −0.64 V versus Ag/AgCl. However, upon cycling, the cell enters into capacity imbalance mainly due to DSAN reacting with water in the presence of carbon felt producing H2. This parasitic reaction makes catholyte the capacity-limiting side. Hence, an in situ electrolysis route is introduced to restore the capacity of the battery in the event of capacity decay. In addition, the use of d-fructose as an additive in the anolyte compartment increases the overpotential for H2 evolution and minimizes capacity fading. Hence, we believe that the work is relevant as it addresses a much bigger problem of parasitic reactions in an alkaline medium and benefits a broader spectrum of work.

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Crossover-free hydroxy-substituted quinone anolyte and potassium ferrocyanide catholyte for aqueous alkaline organic redox flow battery

Cited by 18 publications

References 22 publications

Investigation of Iron(III) Tetraphenylporphyrin as a Redox Flow Battery Anolyte: Unexpected Side Reactivity with the Electrolyte

Investigation of Iron(III) Tetraphenylporphyrin as a Redox Flow Battery Anolyte: Unexpected Side Reactivity with the Electrolyte

Family Tree for Aqueous Organic Redox Couples for Redox Flow Battery Electrolytes: A Conceptual Review

On Capacity Upgradation and In Situ Capacity Rebalancing in Anthrarufin-Based Alkaline Redox Flow Batteries

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