skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones

Abstract

Quinones are appealing targets as organic electrolytes for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series water-soluble quinones, with redox potentials ranging from 605–885 mV vs. NHE, under acidic aqueous conditions (1 M H2SO4). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone-2,7-disulfonate (AQDS) as the anodic electrolyte. The RFB data complement the solution stability measures and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improve organic electrolytes for aqueous RFBs. The authors thank Joseph Fourie for assisting in the synthesis of compound 8. Financial support for this work was provided by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (SSS, TWR, JBG, CWA, YP), with supplemental contributions by the Wisconsin Alumni Research Foundation (WARF) through the WARF Accelerator Program (YQ and partialmore » support for JBG, CWA, YP). NMR spectroscopy facilities were partially supported by the NSF (CHE-0342998 and CHE-1048642), a UW Madison Instructional Laboratory Modernization Award, and a gift from Paul J. and Margaret M. Bender.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [5];  [1];  [1]
  1. University of Wisconsin-Madison
  2. Sandia National Laboratory
  3. Electrosynthesis Company, Inc.
  4. Electrosynthesis Company Inc.
  5. Iowa State University
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1706729
Report Number(s):
PNNL-SA-150888
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 20
Country of Publication:
United States
Language:
English
Subject:
aqueous flow batteries, quinones, organic, redox mediators, energy storage

Citation Formats

Gerken, James B., Anson, Colin W., Preger, Yuliya, Symons, Peter G., Genders, J D., Qui, Yang, Li, Wenzhen, Root, Thatcher W., and Stahl, Shannon S. Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones. United States: N. p., 2020. Web. doi:10.1002/aenm.202000340.
Gerken, James B., Anson, Colin W., Preger, Yuliya, Symons, Peter G., Genders, J D., Qui, Yang, Li, Wenzhen, Root, Thatcher W., & Stahl, Shannon S. Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones. United States. https://doi.org/10.1002/aenm.202000340
Gerken, James B., Anson, Colin W., Preger, Yuliya, Symons, Peter G., Genders, J D., Qui, Yang, Li, Wenzhen, Root, Thatcher W., and Stahl, Shannon S. Tue . "Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones". United States. https://doi.org/10.1002/aenm.202000340.
@article{osti_1706729,
title = {Comparison of Quinone-Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long-Term Stability with Tetrasubstituted Quinones},
author = {Gerken, James B. and Anson, Colin W. and Preger, Yuliya and Symons, Peter G. and Genders, J D. and Qui, Yang and Li, Wenzhen and Root, Thatcher W. and Stahl, Shannon S.},
abstractNote = {Quinones are appealing targets as organic electrolytes for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series water-soluble quinones, with redox potentials ranging from 605–885 mV vs. NHE, under acidic aqueous conditions (1 M H2SO4). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone-2,7-disulfonate (AQDS) as the anodic electrolyte. The RFB data complement the solution stability measures and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improve organic electrolytes for aqueous RFBs. The authors thank Joseph Fourie for assisting in the synthesis of compound 8. Financial support for this work was provided by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (SSS, TWR, JBG, CWA, YP), with supplemental contributions by the Wisconsin Alumni Research Foundation (WARF) through the WARF Accelerator Program (YQ and partial support for JBG, CWA, YP). NMR spectroscopy facilities were partially supported by the NSF (CHE-0342998 and CHE-1048642), a UW Madison Instructional Laboratory Modernization Award, and a gift from Paul J. and Margaret M. Bender.},
doi = {10.1002/aenm.202000340},
url = {https://www.osti.gov/biblio/1706729}, journal = {Advanced Energy Materials},
number = 20,
volume = 10,
place = {United States},
year = {2020},
month = {5}
}

Works referenced in this record:

Electrochemical Energy Storage for Green Grid
journal, May 2011


Flow Batteries: Current Status and Trends
journal, September 2015


Which Parameter is Governing for Aqueous Redox Flow Batteries with Organic Active Material?
journal, March 2019


The Critical Role of Supporting Electrolyte Selection on Flow Battery Cost
journal, January 2017


The Chemistry of Redox-Flow Batteries
journal, June 2015


Vanadium, recent advancements and research prospects: A review
journal, July 2015


Materials and Systems for Organic Redox Flow Batteries: Status and Challenges
journal, August 2017


Recent developments in organic redox flow batteries: A critical review
journal, August 2017


Status and Prospects of Organic Redox Flow Batteries toward Sustainable Energy Storage
journal, August 2019


Quinone 1 e and 2 e /2 H + Reduction Potentials: Identification and Analysis of Deviations from Systematic Scaling Relationships
journal, November 2016


Computational design of molecules for an all-quinone redox flow battery
journal, January 2015


Bio-Inspired Electroactive Organic Molecules for Aqueous Redox Flow Batteries. 1. Thiophenoquinones
journal, September 2015


Molecular engineering of organic electroactive materials for redox flow batteries
journal, January 2018


A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries
journal, June 2018


Symmetric All-Quinone Aqueous Battery
journal, May 2019


A metal-free organic–inorganic aqueous flow battery
journal, January 2014


A New Michael-Reaction-Resistant Benzoquinone for Aqueous Organic Redox Flow Batteries
journal, January 2017


High-Performance Aqueous Organic Flow Battery with Quinone-Based Redox Couples at Both Electrodes
journal, January 2016


An Inexpensive Aqueous Flow Battery for Large-Scale Electrical Energy Storage Based on Water-Soluble Organic Redox Couples
journal, January 2014


An Organic Electroactive Material for Flow Batteries
journal, February 2016


Understanding and Mitigating Capacity Fade in Aqueous Organic Redox Flow Batteries
journal, January 2018


A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte
journal, November 2019


Novel Quinone-Based Couples for Flow Batteries
journal, May 2013


The acid-catalysed oligomerisation of p-benzoquinone
journal, January 1979


Efficient electrochemical synthesis of robust, densely functionalized water soluble quinones
journal, January 2020


Oxidation Processes. XIII. 1 The Inhibitory Action of Sulfite and other Compounds in the Autoxidation of Hydroquinone and its Homologs
journal, February 1939


Novel Catalysis of Hydroquinone Autoxidation with Nitrogen Oxides
journal, May 1994


Mapping the frontiers of quinone stability in aqueous media: implications for organic aqueous redox flow batteries
journal, January 2019


The Chemistry of Anthraquinone.
journal, April 1929


The Chemistry of Esters of Leuco Vat Dyes VI-The Supposed Production of Semiquinone Esters
journal, February 1966


Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility
journal, December 2016


Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods
journal, January 2018


High Power Density Redox Flow Battery Cells
journal, May 2013


High-Performance Vanadium Redox Flow Batteries with Graphite Felt Electrodes
journal, January 2018