Evaluating aqueous flow battery electrolytes: a coordinated approach

Robb, Brian H.; Waters, Scott E.; Marshak, Michael P.

doi:10.1039/d0dt02462g

Evaluating aqueous flow battery electrolytes: a coordinated approach

Journal Article · Mon Oct 26 00:00:00 EDT 2020 · Dalton Transactions

DOI:https://doi.org/10.1039/d0dt02462g· OSTI ID:1848332

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Univ. of Colorado, Boulder, CO (United States); OSTI
Univ. of Colorado, Boulder, CO (United States)

Here, we outline some basic pitfalls in the electrochemical investigation of aqueous metal complexes and advocate for the use of bulk electrolysis in redox flow cells for electrolyte analysis. We demonstrate the methods of operation and performance of a lab scale redox flow battery (RFB), which is assembled from unmodified, commercially available material and cycled with a vanadium electrolyte in order to provide a comparative baseline of expected performance. Common misconceptions about the thermodynamic window for water splitting are addressed and further express the need to develop next-generation aqueous redox flow battery electrolytes. Although non-aqueous electrolytes are a popular approach, they suffer from distinct challenges that limit energy and power density in comparison with aqueous electrolytes. Expanding the scope of aqueous electrolytes to include metal–chelate complexes allows electrolytes to be as tailorable as organic species, while maintaining robust metal-based redox processes. A flow battery assembly and operation guide is provided to help facilitate the use of flow battery testing in the evaluation of next-generation electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AR0000994

OSTI ID:: 1848332

Alternate ID(s):: OSTI ID: 1716540

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 45 Vol. 49; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Recent Progress in Redox Flow Battery Research and Development Wang, Wei; Luo, Qingtao; Li, Bin Advanced Functional Materials, Vol. 23, Issue 8, p. 970-986 https://doi.org/10.1002/adfm.201200694	journal	September 2012
A Stable Vanadium Redox-Flow Battery with High Energy Density for Large-Scale Energy Storage Li, Liyu; Kim, Soowhan; Wang, Wei Advanced Energy Materials, Vol. 1, Issue 3, p. 394-400 https://doi.org/10.1002/aenm.201100008	journal	March 2011
Application of Redox Non-Innocent Ligands to Non-Aqueous Flow Battery Electrolytes Cappillino, Patrick J.; Pratt, Harry D.; Hudak, Nicholas S. Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300566	journal	September 2013
Anthraquinone Derivatives in Aqueous Flow Batteries Gerhardt, Michael R.; Tong, Liuchuan; Gómez-Bombarelli, Rafael Advanced Energy Materials, Vol. 7, Issue 8 https://doi.org/10.1002/aenm.201601488	journal	December 2016
Aqueous Chemistry of Titanium(II) Species Kölle, Ulrich; Kölle, Philipp Angewandte Chemie International Edition, Vol. 42, Issue 37 https://doi.org/10.1002/anie.200351280	journal	September 2003
A Dual‐Ion Organic Symmetric Battery Constructed from Phenazine‐Based Artificial Bipolar Molecules Dai, Gaole; He, Yan; Niu, Zhihui Angewandte Chemie International Edition, Vol. 58, Issue 29 https://doi.org/10.1002/anie.201901040	journal	July 2019
Understanding Aqueous Electrolyte Stability through Combined Computational and Magnetic Resonance Spectroscopy: A Case Study on Vanadium Redox Flow Battery Electrolytes Vijayakumar, Murugesan; Nie, Zimin; Walter, Eric ChemPlusChem, Vol. 80, Issue 2 https://doi.org/10.1002/cplu.201402139	journal	September 2014
A rechargeable redox battery utilizing ruthenium complexes with non-aqueous organic electrolyte Matsuda, Y.; Tanaka, K.; Okada, M. Journal of Applied Electrochemistry, Vol. 18, Issue 6, p. 909-914 https://doi.org/10.1007/BF01016050	journal	November 1988
A study of the V(II)/V(III) redox couple for redox flow cell applications Sum, E.; Skyllas-Kazacos, M. Journal of Power Sources, Vol. 15, Issue 2-3, p. 179-190 https://doi.org/10.1016/0378-7753(85)80071-9	journal	June 1985
Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hajimu Electrochimica Acta, Vol. 48, Issue 1, p. 43-50 https://doi.org/10.1016/S0013-4686(02)00546-7	journal	November 2002
Structure and properties of iron(III) 1,3-propanediaminetetraacetate complex in aqueous solutions Kanamori, Kan; Ukita, Naoya; Kawai, Kiyoyasu Inorganica Chimica Acta, Vol. 186, Issue 2 https://doi.org/10.1016/S0020-1693(00)85422-5	journal	August 1991
Quantum jumps in the PEMFC science and technology from the 1960s to the year 2000 Costamagna, Paola; Srinivasan, Supramaniam Journal of Power Sources, Vol. 102, Issue 1-2 https://doi.org/10.1016/S0378-7753(01)00807-2	journal	December 2001
Solubility of vanadyl sulfate in concentrated sulfuric acid solutions Rahman, F.; Skyllas-Kazacos, M. Journal of Power Sources, Vol. 72, Issue 2 https://doi.org/10.1016/S0378-7753(97)02692-X	journal	April 1998
Redox chemistry of aquatitanium(II), Ti2+(aq) Gould, Edwin S. Coordination Chemistry Reviews, Vol. 255, Issue 23-24 https://doi.org/10.1016/j.ccr.2011.06.006	journal	December 2011
Aqueous organic and redox-mediated redox flow batteries: a review Gentil, Solène; Reynard, Danick; Girault, Hubert H. Current Opinion in Electrochemistry, Vol. 21 https://doi.org/10.1016/j.coelec.2019.12.006	journal	June 2020
Non-aqueous vanadium acetylacetonate electrolyte for redox flow batteries Liu, Qinghua; Sleightholme, Alice E. S.; Shinkle, Aaron A. Electrochemistry Communications, Vol. 11, Issue 12, p. 2312-2315 https://doi.org/10.1016/j.elecom.2009.10.006	journal	December 2009
Non-aqueous chromium acetylacetonate electrolyte for redox flow batteries Liu, Qinghua; Shinkle, Aaron A.; Li, Yongdan Electrochemistry Communications, Vol. 12, Issue 11, p. 1634-1637 https://doi.org/10.1016/j.elecom.2010.09.013	journal	November 2010
Ionic liquid-mediated aqueous redox flow batteries for high voltage applications Chen, Ruiyong; Hempelmann, Rolf Electrochemistry Communications, Vol. 70 https://doi.org/10.1016/j.elecom.2016.07.003	journal	September 2016
Stability of molecular radicals in organic non-aqueous redox flow batteries: A mini review Armstrong, Craig G.; Toghill, Kathryn E. Electrochemistry Communications, Vol. 91 https://doi.org/10.1016/j.elecom.2018.04.017	journal	June 2018
A study of the Fe(III)/Fe(II)–triethanolamine complex redox couple for redox flow battery application Wen, Y. H.; Zhang, H. M.; Qian, P. Electrochimica Acta, Vol. 51, Issue 18, p. 3769-3775 https://doi.org/10.1016/j.electacta.2005.10.040	journal	May 2006
Corrosion behavior of a positive graphite electrode in vanadium redox flow battery Liu, Huijun; Xu, Qian; Yan, Chuanwei Electrochimica Acta, Vol. 56, Issue 24 https://doi.org/10.1016/j.electacta.2011.07.083	journal	October 2011
Electrochemistry of the tris(2,2‘-bipyridine) complex of iron(II) in ionic liquids and aprotic molecular solvents Cabral, Diogo Moulin; Howlett, Patrick C.; MacFarlane, Douglas R. Electrochimica Acta, Vol. 220 https://doi.org/10.1016/j.electacta.2016.10.126	journal	December 2016
High Performance Redox Flow Batteries: An Analysis of the Upper Performance Limits of Flow Batteries Using Non-aqueous Solvents Sun, C. -N.; Mench, M. M.; Zawodzinski, T. A. Electrochimica Acta, Vol. 237 https://doi.org/10.1016/j.electacta.2017.03.132	journal	May 2017
A comprehensive review on PEM water electrolysis Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934 https://doi.org/10.1016/j.ijhydene.2013.01.151	journal	April 2013
Unprecedented Capacity and Stability of Ammonium Ferrocyanide Catholyte in pH Neutral Aqueous Redox Flow Batteries Luo, Jian; Hu, Bo; Debruler, Camden Joule, Vol. 3, Issue 1 https://doi.org/10.1016/j.joule.2018.10.010	journal	January 2019
Chelated Chromium Electrolyte Enabling High-Voltage Aqueous Flow Batteries Robb, Brian H.; Farrell, Jason M.; Marshak, Michael P. Joule, Vol. 3, Issue 10 https://doi.org/10.1016/j.joule.2019.07.002	journal	October 2019
Vanadium redox battery: Positive half-cell electrolyte studies Rahman, Faizur; Skyllas-Kazacos, Maria Journal of Power Sources, Vol. 189, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.12.113	journal	April 2009
Non-aqueous manganese acetylacetonate electrolyte for redox flow batteries Sleightholme, Alice E. S.; Shinkle, Aaron A.; Liu, Qinghua Journal of Power Sources, Vol. 196, Issue 13, p. 5742-5745 https://doi.org/10.1016/j.jpowsour.2011.02.020	journal	July 2011
Dramatic performance gains in vanadium redox flow batteries through modified cell architecture Aaron, D. S.; Liu, Q.; Tang, Z. Journal of Power Sources, Vol. 206 https://doi.org/10.1016/j.jpowsour.2011.12.026	journal	May 2012
Cost and performance model for redox flow batteries Viswanathan, Vilayanur; Crawford, Alasdair; Stephenson, David Journal of Power Sources, Vol. 247 https://doi.org/10.1016/j.jpowsour.2012.12.023	journal	February 2014
A comparative study of all-vanadium and iron-chromium redox flow batteries for large-scale energy storage Zeng, Y. K.; Zhao, T. S.; An, L. Journal of Power Sources, Vol. 300 https://doi.org/10.1016/j.jpowsour.2015.09.100	journal	December 2015
Recent developments in organic redox flow batteries: A critical review Leung, P.; Shah, A. A.; Sanz, L. Journal of Power Sources, Vol. 360 https://doi.org/10.1016/j.jpowsour.2017.05.057	journal	August 2017
The 5-V Window of Polarizability of Fluorinated Diamond Electrodes in Aqueous Solutions Ferro, Sergio; De Battisti, Achille Analytical Chemistry, Vol. 75, Issue 24 https://doi.org/10.1021/ac034717r	journal	December 2003
Poly(boron-dipyrromethene)—A Redox-Active Polymer Class for Polymer Redox-Flow Batteries Winsberg, Jan; Hagemann, Tino; Muench, Simon Chemistry of Materials, Vol. 28, Issue 10 https://doi.org/10.1021/acs.chemmater.6b00640	journal	May 2016
Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review Kwabi, David G.; Ji, Yunlong; Aziz, Michael J. Chemical Reviews, Vol. 120, Issue 14 https://doi.org/10.1021/acs.chemrev.9b00599	journal	February 2020
Electronic Structure and Reactivity of a Well-Defined Mononuclear Complex of Ti(II) Wijeratne, Gayan B.; Zolnhofer, Eva M.; Fortier, Skye Inorganic Chemistry, Vol. 54, Issue 21 https://doi.org/10.1021/acs.inorgchem.5b01796	journal	October 2015
Elucidating Factors Controlling Long-Term Stability of Radical Anions for Negative Charge Storage in Nonaqueous Redox Flow Batteries Zhang, Jingjing; Huang, Jinhua; Robertson, Lily A. The Journal of Physical Chemistry C, Vol. 122, Issue 15 https://doi.org/10.1021/acs.jpcc.8b01434	journal	March 2018
Solution Properties and Practical Limits of Concentrated Electrolytes for Nonaqueous Redox Flow Batteries Zhang, Jingjing; Corman, R. E.; Schuh, Jonathon K. The Journal of Physical Chemistry C, Vol. 122, Issue 15 https://doi.org/10.1021/acs.jpcc.8b02009	journal	March 2018
Polymeric Active Materials for Redox Flow Battery Application Lai, Yun Yu; Li, Xiang; Zhu, Yu ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b00864	journal	December 2019
Effect of Chelation on Iron–Chromium Redox Flow Batteries Waters, Scott E.; Robb, Brian H.; Marshak, Michael P. ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00761	journal	April 2020
Rediscovering Cr ₂ O ₇ ^2– , an Oxidant with Unrivaled Power and Energy Density, for Affordable, Next-Generation Energy Storage and Conversion Finkelstein, David A.; Abruña, Héctor D. ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00274	journal	May 2017
Electrochemical Energy Storage for Green Grid Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W. Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613 https://doi.org/10.1021/cr100290v	journal	May 2011
Proton-Coupled Electron Transfer Weinberg, David R.; Gagliardi, Christopher J.; Hull, Jonathan F. Chemical Reviews, Vol. 112, Issue 7 https://doi.org/10.1021/cr200177j	journal	April 2012
Flow Batteries: Current Status and Trends Soloveichik, Grigorii L. Chemical Reviews, Vol. 115, Issue 20 https://doi.org/10.1021/cr500720t	journal	September 2015
On the Standard Potential of the Titanium(III)-Titanium(II) Couple Olver, John W.; Ross, James W. Journal of the American Chemical Society, Vol. 85, Issue 17 https://doi.org/10.1021/ja00900a006	journal	September 1963
The structure of iron(III) in aqueous solution Schugar, Harvey J.; Walling, Cheves.; Jones, Rebecca B. Journal of the American Chemical Society, Vol. 89, Issue 15 https://doi.org/10.1021/ja00991a007	journal	July 1967
Voltammetry of Quinones in Unbuffered Aqueous Solution: Reassessing the Roles of Proton Transfer and Hydrogen Bonding in the Aqueous Electrochemistry of Quinones Quan, May; Sanchez, Daniel; Wasylkiw, Mark F. Journal of the American Chemical Society, Vol. 129, Issue 42, p. 12847-12856 https://doi.org/10.1021/ja0743083	journal	October 2007
Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications Stauber, Julia M.; Zhang, Shiyu; Gvozdik, Nataliya Journal of the American Chemical Society, Vol. 140, Issue 2 https://doi.org/10.1021/jacs.7b08751	journal	January 2018
A metal-free organic–inorganic aqueous flow battery Huskinson, Brian; Marshak, Michael P.; Suh, Changwon Nature, Vol. 505, Issue 7482, p. 195-198 https://doi.org/10.1038/nature12909	journal	January 2014
An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials Janoschka, Tobias; Martin, Norbert; Martin, Udo Nature, Vol. 527, Issue 7576, p. 78-81 https://doi.org/10.1038/nature15746	journal	October 2015
A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries Hollas, Aaron; Wei, Xiaoliang; Murugesan, Vijayakumar Nature Energy, Vol. 3, Issue 6 https://doi.org/10.1038/s41560-018-0167-3	journal	June 2018
Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries Darling, Robert M.; Gallagher, Kevin G.; Kowalski, Jeffrey A. Energy & Environmental Science, Vol. 7, Issue 11, p. 3459-3477 https://doi.org/10.1039/C4EE02158D	journal	January 2014
Towards an all-copper redox flow battery based on a copper-containing ionic liquid Schaltin, Stijn; Li, Yun; Brooks, Neil R. Chemical Communications, Vol. 52, Issue 2 https://doi.org/10.1039/C5CC06774J	journal	January 2016
Nonaqueous redox-flow batteries: organic solvents, supporting electrolytes, and redox pairs Gong, Ke; Fang, Qianrong; Gu, Shuang Energy & Environmental Science, Vol. 8, Issue 12, p. 3515-3530 https://doi.org/10.1039/C5EE02341F	journal	January 2015
Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries VanGelder, L. E.; Kosswattaarachchi, A. M.; Forrestel, P. L. Chemical Science, Vol. 9, Issue 6 https://doi.org/10.1039/C7SC05295B	journal	January 2018
Desymmetrized hexasubstituted [3]radialene anions as aqueous organic catholytes for redox flow batteries Turner, Nicholas A.; Freeman, Matthew B.; Pratt, Harry D. Chemical Communications, Vol. 56, Issue 18 https://doi.org/10.1039/C9CC08547E	journal	January 2020
Alkaline quinone flow battery Lin, K.; Chen, Q.; Gerhardt, M. R. Science, Vol. 349, Issue 6255, p. 1529-1532 https://doi.org/10.1126/science.aab3033	journal	September 2015
Minimizing Oxygen Permeation in Metal-Chelate Flow Batteries Robb, Brian H.; Waters, Scott E.; Marshak, Michael P. ECS Transactions, Vol. 97, Issue 7 https://doi.org/10.1149/09707.0237ecst	journal	June 2020
Aqueous Redox Transition Metal Complexes for Electrochemical Applications as a Function of pH Ibanez, Jorge G.; Choi, Chan‐Soo; Becker, Ralph S. Journal of The Electrochemical Society, Vol. 134, Issue 12 https://doi.org/10.1149/1.2100344	journal	December 1987
New All-Vanadium Redox Flow Cell Skyllas-Kazacos, M. Journal of The Electrochemical Society, Vol. 133, Issue 5 https://doi.org/10.1149/1.2108706	journal	January 1986
Progress in Flow Battery Research and Development Skyllas-Kazacos, M.; Chakrabarti, M. H.; Hajimolana, S. A. Journal of The Electrochemical Society, Vol. 158, Issue 8, p. R55-R79 https://doi.org/10.1149/1.3599565	journal	June 2011
Communication—Iron Ionic Liquid Electrolytes for Redox Flow Battery Applications Miller, M. A.; Wainright, J. S.; Savinell, R. F. Journal of The Electrochemical Society, Vol. 163, Issue 3 https://doi.org/10.1149/2.0061605jes	journal	January 2016
Advanced Redox-Flow Batteries: A Perspective Perry, Mike L.; Weber, Adam Z. Journal of The Electrochemical Society, Vol. 163, Issue 1 https://doi.org/10.1149/2.0101601jes	journal	September 2015
Non-Aqueous Redox Flow Batteries with Nickel and Iron Tris(2,2ʹ-bipyridine) Complex Electrolyte Mun, Junyoung; Lee, Myung-Jin; Park, Joung-Won Electrochemical and Solid-State Letters, Vol. 15, Issue 6 https://doi.org/10.1149/2.033206esl	journal	January 2012
Spectroelectrochemistry of Vanadium Acetylacetonate and Chromium Acetylacetonate for Symmetric Nonaqueous Flow Batteries Saraidaridis, James D.; Bartlett, Bart M.; Monroe, Charles W. Journal of The Electrochemical Society, Vol. 163, Issue 7 https://doi.org/10.1149/2.0441607jes	journal	January 2016
Highly Soluble Tris(2,2’-bipyridine) Metal Bis(trifluoromethanesulfonyl)imide Complexes for High Energy Organic Redox Flow Batteries Mun, Junyoung; Oh, Duk-Jin; Park, Min Sik Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0791802jes	journal	January 2018
Electrochemistry in Room Temperature Ionic Liquids: A Review and Some Possible Applications Silvester, Debbie S.; Compton, Richard G. Zeitschrift für Physikalische Chemie, Vol. 220, Issue 10, p. 1247-1274 https://doi.org/10.1524/zpch.2006.220.10.1247	journal	October 2006

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