Multifaceted effects of ring fusion on the stability of charged dialkoxyarene redoxmers

Li, Zhiguang; Jeong, Heonjae; Fang, Xiaoting; Zhao, Yuyue; Robertson, Lily A.; Zhang, Jingjing; Shkrob, Ilya A.; Cheng, Lei; Wei, Xiaoliang; Zhang, Lu

doi:10.1016/j.jpowsour.2024.234689

Multifaceted effects of ring fusion on the stability of charged dialkoxyarene redoxmers

Journal Article · Thu May 09 00:00:00 EDT 2024 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2024.234689· OSTI ID:2562127

Li, Zhiguang ^[1]; ^[2]; Fang, Xiaoting ^[1]; Zhao, Yuyue ^[3]; ^[4]; Zhang, Jingjing ^[4]; Shkrob, Ilya A. ^[4]; Cheng, Lei ^[4]; ^[5]; ^[4]

Indiana University-Purdue University Indianapolis (IUPUI), Indianapolis, IN (United States); Purdue University, West Lafayette, IN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); Gachon University, Seongnam (Korea, Republic of)
Indiana University-Purdue University Indianapolis (IUPUI), Indianapolis, IN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Indiana University-Purdue University Indianapolis (IUPUI), Indianapolis, IN (United States)

Due to their almost unlimited scalability, redox flow batteries can make versatile and affordable energy storage systems. Redox active materials (redoxmers) in these batteries largely define their electrochemical performance, including the life span of the battery that depends on the stability of charged redoxmers. Here, in this study, we examine the effects of expanding the pi-system in the arene rings on the chemical stability of dialkoxyarene redoxmers that are used to store positive charge in RFBs. When 1,4-dimethoxybenzene is pi-extended to 1,4 dimethoxynaphthalene, a lower redox potential, improved kinetic stability, and longer cycling life are observed. However, when an additional ring is fused to make 9,10-dimethoxyanthracene, the radical cation undergoes rapid O -dealkylation possibly due to increased steric strain that drives methoxy out of the arene plane thus breaking the pi-conjugation with O 2p orbitals. On the other hand, the planar structure of 1,4-dimethoxynaphthalene may facilitate second -order reactions of radical cations leading to their neutralization in the bulk. Our study suggests that extending the pi-system changes reactivity in multiple (sometimes, opposite) ways, so lowering the oxidation potential through pi-conjugation to improve redoxmer stability should be pursued with caution.

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); USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR); USDOE Office of Science (SC), Engineering & Technology. Office of Small Business Innovation Research (SBIR) and Small Business Technology Transfer (STTR) Programs

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2562127

Alternate ID(s):: OSTI ID: 2349149

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 608; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery Wei, Xiaoliang; Xu, Wu; Huang, Jinhua Angewandte Chemie International Edition, Vol. 54, Issue 30 https://doi.org/10.1002/anie.201501443	journal	April 2015
Redox-Flow Batteries: From Metals to Organic Redox-Active Materials Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201604925	journal	November 2016
A π-Conjugation Extended Viologen as a Two-Electron Storage Anolyte for Total Organic Aqueous Redox Flow Batteries Luo, Jian; Hu, Bo; Debruler, Camden Angewandte Chemie International Edition, Vol. 57, Issue 1 https://doi.org/10.1002/anie.201710517	journal	December 2017
Electrochemical polymerization of paradialkoxybenzenes Le Berre, Véronique; Angely, Lysiane; Simonet, Jacques Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 218, Issue 1-2 https://doi.org/10.1016/0022-0728(87)87014-6	journal	February 1987
Comparing calendar and cycle life stability of redox active organic molecules for nonaqueous redox flow batteries Zhang, Jingjing; Huang, Jinhua; Robertson, Lily A. Journal of Power Sources, Vol. 397 https://doi.org/10.1016/j.jpowsour.2018.07.001	journal	September 2018
Comparative Study of Organic Radical Cation Stability and Coulombic Efficiency for Nonaqueous Redox Flow Battery Applications Attanayake, N. Harsha; Suduwella, T. Malsha; Yan, Yichao The Journal of Physical Chemistry C, Vol. 125, Issue 26 https://doi.org/10.1021/acs.jpcc.1c00686	journal	June 2021
Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations Assary, Rajeev S.; Zhang, Lu; Huang, Jinhua The Journal of Physical Chemistry C, Vol. 120, Issue 27 https://doi.org/10.1021/acs.jpcc.6b04263	journal	June 2016
Toward Improved Catholyte Materials for Redox Flow Batteries: What Controls Chemical Stability of Persistent Radical Cations? Zhang, Jingjing; Shkrob, Ilya A.; Assary, Rajeev S. The Journal of Physical Chemistry C, Vol. 121, Issue 42 https://doi.org/10.1021/acs.jpcc.7b08281	journal	October 2017
On Transferability of Performance Metrics for Redox-Active Molecules Silcox, Benjamin; Zhang, Jingjing; Shkrob, Ilya A. The Journal of Physical Chemistry C, Vol. 123, Issue 27 https://doi.org/10.1021/acs.jpcc.9b02230	journal	June 2019
Effective Design Strategy of Small Bipolar Molecules through Fused Conjugation toward 2.5 V Based Redox Flow Batteries Liu, Yue; Dai, Gaole; Chen, Yuanyuan ACS Energy Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acsenergylett.2c00198	journal	March 2022
“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
Status and Prospects of Organic Redox Flow Batteries toward Sustainable Energy Storage Luo, Jian; Hu, Bo; Hu, Maowei ACS Energy Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsenergylett.9b01332	journal	August 2019
Molecular Design of Fused-Ring Phenazine Derivatives for Long-Cycling Alkaline Redox Flow Batteries Wang, Caixing; Li, Xiang; Yu, Bo ACS Energy Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsenergylett.9b02676	journal	January 2020
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
Flow Batteries: Current Status and Trends Soloveichik, Grigorii L. Chemical Reviews, Vol. 115, Issue 20 https://doi.org/10.1021/cr500720t	journal	September 2015
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
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
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
A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR Duan, Wentao; Vemuri, Rama S.; Milshtein, Jarrod D. Journal of Materials Chemistry A, Vol. 4, Issue 15 https://doi.org/10.1039/C6TA01177B	journal	January 2016
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
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Synthesis and Characterization of Semiconductive Poly‐1,4‐Dimethoxybenzene and Its Derived Polyquinone Foos, J. S.; Erker, S. M.; Rembetsy, L. M. Journal of The Electrochemical Society, Vol. 133, Issue 4 https://doi.org/10.1149/1.2108689	journal	April 1986
Understanding the Stability of Aromatic Redox Shuttles for Overcharge Protection of Lithium-Ion Cells Chen, Zonghai; Wang, Qingzheng; Amine, K. Journal of The Electrochemical Society, Vol. 153, Issue 12 https://doi.org/10.1149/1.2352048	journal	January 2006
Anodic generation of new ionophoric conducting polymers Simonet, J. Pure and Applied Chemistry, Vol. 70, Issue 6 https://doi.org/10.1351/pac199870061253	journal	June 1998

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Multifaceted effects of ring fusion on the stability of charged dialkoxyarene redoxmers

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