Concentration‐dependent Cycling of Phenothiazine‐based Electrolytes in Nonaqueous Redox Flow Cells

Kaur, Aman Preet; Neyhouse, Bertrand J.; Shkrob, Ilya A.; Wang, Yilin; Attanayake, N. Harsha; Jha, Rahul Kant; Wu, Qianwen; Zhang, Lu; Ewoldt, Randy H.; Brushett, Fikile R.; Odom, Susan A.

doi:10.1002/asia.202201171

Concentration‐dependent Cycling of Phenothiazine‐based Electrolytes in Nonaqueous Redox Flow Cells

Journal Article · Wed Jan 11 00:00:00 EST 2023 · Chemistry - An Asian Journal

DOI:https://doi.org/10.1002/asia.202201171· OSTI ID:2205070

^[1]; ^[2]; ^[3]; ^[4]; ^[1]; ^[1]; Wu, Qianwen ^[4]; Zhang, Lu ^[3]; Ewoldt, Randy H. ^[4]; ^[2]; ^[1]

University of Kentucky, Lexington, KY (United States)
Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
University of Illinois, Urbana-Champaign, IL (United States)

Increasing redox-active species concentrations can improve viability for organic redox flow batteries by enabling higher energy densities, but the required concentrated solutions can become viscous and less conductive, leading to inefficient electrochemical cycling and low material utilization at higher current densities. To better understand these tradeoffs in a model system, we study a highly soluble and stable redox-active couple, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT), and its bis(trifluoromethanesulfonyl)imide radical cation salt (MEEPT-TFSI). We measure the physicochemical properties of electrolytes containing 0.2–1 M active species and connect these to symmetric cell cycling behavior, achieving robust cycling performance. Specifically, for a 1 M electrolyte concentration, we demonstrate 94% materials utilization, 89% capacity retention, and 99.8% average coulombic efficiency over 435 h (100 full cycles). This demonstration helps to establish potential for high-performing, concentrated nonaqueous electrolytes and highlights possible failure modes in such systems.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES), Joint Center for Energy Storage Research (JCESR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2205070

Journal Information:: Chemistry - An Asian Journal, Journal Name: Chemistry - An Asian Journal Journal Issue: 5 Vol. 18; ISSN 1861-4728

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

A Highly Concentrated Catholyte Based on a Solvate Ionic Liquid for Rechargeable Flow Batteries Takechi, Kensuke; Kato, Yuichi; Hase, Yoko Advanced Materials, Vol. 27, Issue 15 https://doi.org/10.1002/adma.201405840	journal	March 2015
Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries Huang, Jinhua; Cheng, Lei; Assary, Rajeev S. Advanced Energy Materials, Vol. 5, Issue 6 https://doi.org/10.1002/aenm.201401782	journal	November 2014
A Highly Soluble Organic Catholyte for Non-Aqueous Redox Flow Batteries Kaur, Aman Preet; Holubowitch, Nicolas E.; Ergun, Selin Energy Technology, Vol. 3, Issue 5, p. 476-480 https://doi.org/10.1002/ente.201500020	journal	April 2015
Bio-inspired Molecular Redesign of a Multi-redox Catholyte for High-Energy Non-aqueous Organic Redox Flow Batteries Kwon, Giyun; Lee, Kyunam; Lee, Myeong Hwan Chem, Vol. 5, Issue 10 https://doi.org/10.1016/j.chempr.2019.07.006	journal	October 2019
Concentration-dependent charge-discharge characteristics of non-aqueous redox flow battery electrolyte combinations Kosswattaarachchi, Anjula M.; Cook, Timothy R. Electrochimica Acta, Vol. 261 https://doi.org/10.1016/j.electacta.2017.12.131	journal	January 2018
Recent Progress in Organic Species for Redox Flow Batteries Li, Zening; Jiang, Taoli; Ali, Mohsin Energy Storage Materials, Vol. 50 https://doi.org/10.1016/j.ensm.2022.04.038	journal	September 2022
Two electron utilization of methyl viologen anolyte in nonaqueous organic redox flow battery Hu, Bo; Liu, T. Leo Journal of Energy Chemistry, Vol. 27, Issue 5 https://doi.org/10.1016/j.jechem.2018.02.014	journal	September 2018
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
Crowded electrolytes containing redoxmers in different states of charge: Solution structure, properties, and fundamental limits on energy density Shkrob, Ilya A.; Robertson, Lily A.; Yu, Zhou Journal of Molecular Liquids, Vol. 334 https://doi.org/10.1016/j.molliq.2021.116533	journal	July 2021
Concentration-Dependent Dimerization of Anthraquinone Disulfonic Acid and Its Impact on Charge Storage Carney, Thomas J.; Collins, Steven J.; Moore, Jeffrey S. Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00616	journal	May 2017
Tailoring Two-Electron-Donating Phenothiazines To Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries Attanayake, N. Harsha; Kowalski, Jeffrey A.; Greco, Katharine V. Chemistry of Materials, Vol. 31, Issue 12 https://doi.org/10.1021/acs.chemmater.8b04770	journal	May 2019
Quantifying Environmental Effects on the Solution and Solid-State Stability of a Phenothiazine Radical Cation Kaur, Aman Preet; Harris, Oliver C.; Attanayake, N. Harsha Chemistry of Materials, Vol. 32, Issue 7 https://doi.org/10.1021/acs.chemmater.9b05345	journal	February 2020
Competitive Pi-Stacking and H-Bond Piling Increase Solubility of Heterocyclic Redoxmers Zhao, Yuyue; Sarnello, Erik S.; Robertson, Lily A. The Journal of Physical Chemistry B, Vol. 124, Issue 46 https://doi.org/10.1021/acs.jpcb.0c07647	journal	November 2020
Self-Assembled Solute Networks in Crowded Electrolyte Solutions and Nanoconfinement of Charged Redoxmer Molecules Shkrob, Ilya A.; Li, Tao; Sarnello, Erik The Journal of Physical Chemistry B, Vol. 124, Issue 45 https://doi.org/10.1021/acs.jpcb.0c07760	journal	October 2020
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
Comparison of Separators vs Membranes in Nonaqueous Redox Flow Battery Electrolytes Containing Small Molecule Active Materials Liang, Zhiming; Attanayake, N. Harsha; Greco, Katharine V. ACS Applied Energy Materials, Vol. 4, Issue 6 https://doi.org/10.1021/acsaem.1c00017	journal	May 2021
PEGylation-Enabled Extended Cyclability of a Non-aqueous Redox Flow Battery Chai, Jingchao; Lashgari, Amir; Cao, Zishu ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.0c01045	journal	March 2020
Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries Li, Min; Odom, Susan A.; Pancoast, Adam R. ACS Energy Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acsenergylett.1c01675	journal	October 2021
“Wine-Dark Sea” in an Organic Flow Battery: Storing Negative Charge in 2,1,3-Benzothiadiazole Radicals Leads to Improved Cyclability Duan, Wentao; Huang, Jinhua; Kowalski, Jeffrey A. ACS Energy Letters, Vol. 2, Issue 5 https://doi.org/10.1021/acsenergylett.7b00261	journal	April 2017
Materials and Systems for Organic Redox Flow Batteries: Status and Challenges Wei, Xiaoliang; Pan, Wenxiao; Duan, Wentao ACS Energy Letters, Vol. 2, Issue 9 https://doi.org/10.1021/acsenergylett.7b00650	journal	August 2017
Highly Soluble 1,4-Diaminoanthraquinone Derivative for Nonaqueous Symmetric Redox Flow Batteries Geysens, Pieter; Li, Yun; Vankelecom, Ivo ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 9 https://doi.org/10.1021/acssuschemeng.9b07244	journal	February 2020
Observation of Microheterogeneity in Highly Concentrated Nonaqueous Electrolyte Solutions Robertson, Lily A.; Li, Zhixia; Cao, Yu Journal of the American Chemical Society https://doi.org/10.1021/jacs.9b02323	journal	May 2019
Developing a Predictive Solubility Model for Monomeric and Oligomeric Cyclopropenium-Based Flow Battery Catholytes Robinson, Sophia G.; Yan, Yichao; Hendriks, Koen H. Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b04270	journal	May 2019
Mechanism-Based Design of a High-Potential Catholyte Enables a 3.2 V All-Organic Nonaqueous Redox Flow Battery Yan, Yichao; Robinson, Sophia G.; Sigman, Matthew S. Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b07345	journal	September 2019
Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility Wedege, Kristina; Dražević, Emil; Konya, Denes Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep39101	journal	December 2016
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
High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries Milshtein, Jarrod D.; Kaur, Aman Preet; Casselman, Matthew D. Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE02027E	journal	January 2016
Dual function organic active materials for nonaqueous redox flow batteries Attanayake, N. Harsha; Liang, Zhiming; Wang, Yilin Materials Advances, Vol. 2, Issue 4 https://doi.org/10.1039/D0MA00881H	journal	January 2021
Recent advancements in rational design of non-aqueous organic redox flow batteries Li, Min; Rhodes, Zayn; Cabrera-Pardo, Jaime R. Sustainable Energy & Fuels, Vol. 4, Issue 9 https://doi.org/10.1039/D0SE00800A	journal	January 2020
New highly soluble triarylamine-based materials as promising catholytes for redox flow batteries Romadina, Elena I.; Volodin, Ivan A.; Stevenson, Keith J. Journal of Materials Chemistry A, Vol. 9, Issue 13 https://doi.org/10.1039/D0TA11860E	journal	January 2021
On the challenges of materials and electrochemical characterization of concentrated electrolytes for redox flow batteries Fenton, Alexis M.; Jha, Rahul Kant; Neyhouse, Bertrand J. Journal of Materials Chemistry A, Vol. 10, Issue 35 https://doi.org/10.1039/D2TA00690A	journal	January 2022
Viscous flow properties and hydrodynamic diameter of phenothiazine-based redox-active molecules in different supporting salt environments Wang, Yilin; Kaur, Aman Preet; Attanayake, N. Harsha Physics of Fluids, Vol. 32, Issue 8 https://doi.org/10.1063/5.0010168	journal	August 2020
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P. Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821672117	journal	June 2020
Transport Property Requirements for Flow Battery Separators Darling, Robert; Gallagher, Kevin; Xie, Wei Journal of The Electrochemical Society, Vol. 163, Issue 1 https://doi.org/10.1149/2.0051601jes	journal	July 2015

Similar Records

Elucidating the Effects of Temperature on Nonaqueous Redox Flow Cell Cycling Performance

Journal Article · Thu Nov 30 19:00:00 EST 2023 · Journal of the Electrochemical Society · OSTI ID:2582816

Decoding the Effect of Anion Identity on the Solubility of N-(2-(2-Methoxyethoxy)ethyl)phenothiazine (MEEPT)

Journal Article · Wed May 21 20:00:00 EDT 2025 · Energy & Fuels · OSTI ID:2589766

Indolo[2,3-b]quinoxaline as a Low Reduction Potential and High Stability Anolyte Scaffold for Nonaqueous Redox Flow Batteries

Journal Article · Tue Aug 15 20:00:00 EDT 2023 · Journal of the American Chemical Society · OSTI ID:2006608

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
flow battery
phenothiazine
redox reaction

Concentration‐dependent Cycling of Phenothiazine‐based Electrolytes in Nonaqueous Redox Flow Cells

Citation Formats

References (34)

Similar Records

Related Subjects