A Phosphonate-Functionalized Quinone Redox Flow Battery at Near-Neutral pH with Record Capacity Retention Rate

Ji, Yunlong; Goulet, Marc-Antoni; Pollack, Daniel A.; Kwabi, David G.; Jin, Shijian; De Porcellinis, Diana; Kerr, Emily F.; Gordan, Roy G.; Aziz, Michael J.

doi:10.1002/aenm.201900039

A Phosphonate-Functionalized Quinone Redox Flow Battery at Near-Neutral pH with Record Capacity Retention Rate

Journal Article · Wed Feb 06 00:00:00 EST 2019 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201900039· OSTI ID:1661884

^[1]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]

Harvard Univ., Cambridge, MA (United States); Harvard John A. Paulson School of Engineering and Applied Sciences
Harvard Univ., Cambridge, MA (United States)

A highly stable phosphonate-functionalized anthraquinone is introduced as the redox-active material in a negative potential electrolyte (negolyte) for aqueous redox flow batteries operating at nearly neutral pH. Here, the design and synthesis of 2,6-DPPEAQ, (((9,10-dioxo-9,10-dihydroanthracene-2,6-diyl)bis(oxy))bis(propane-3,1-diyl))bis(phosphonic acid), which has a high solubility at pH 9 and above, is described. Chemical stability studies demonstrate high stability at both pH 9 and 12. By pairing 2,6-DPPEAQ with a potassium ferri/ferrocyanide positive electrolyte across an inexpensive, nonfluorinated permselective polymer membrane, this near-neutral quinone flow battery exhibits an open-circuit voltage of 1.0 V and a capacity fade rate of 0.00036% per cycle and 0.014% per day, which is the lowest ever reported for any flow battery in the absence of rebalancing processes. It is further demonstrated that the negolyte pH drifts upward upon atmospheric oxygen penetration but, when oxygen is excluded, oscillates reversibly between 9 and 12 during cycling. These results enhance the suitability of aqueous-soluble redox-active organics for use in large-scale energy storage, potentially enabling massive penetration of intermittent renewable electricity.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Sciences (SEAS); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: Innovation Fund Denmark; Massachusetts Clean Energy Technology Center; National Science Foundation; USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1661884

Alternate ID(s):: OSTI ID: 1493638

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 12 Vol. 9; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Poly(TEMPO)/Zinc Hybrid-Flow Battery: A Novel, “Green,” High Voltage, and Safe Energy Storage System Winsberg, Jan; Janoschka, Tobias; Morgenstern, Sabine Advanced Materials, Vol. 28, Issue 11 https://doi.org/10.1002/adma.201505000	journal	January 2016
A Total Organic Aqueous Redox Flow Battery Employing a Low Cost and Sustainable Methyl Viologen Anolyte and 4-HO-TEMPO Catholyte Liu, Tianbiao; Wei, Xiaoliang; Nie, Zimin Advanced Energy Materials, Vol. 6, Issue 3, 1501449 https://doi.org/10.1002/aenm.201501449	journal	December 2015
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
Alkaline Benzoquinone Aqueous Flow Battery for Large-Scale Storage of Electrical Energy Yang, Zhengjin; Tong, Liuchuan; Tabor, Daniel P. Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201702056	journal	December 2017
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery Wei, Xiaoliang; Xu, Wu; Huang, Jinhua Angewandte Chemie, Vol. 127, Issue 30 https://doi.org/10.1002/ange.201501443	journal	April 2015
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
Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In ₂ O ₃ Films Using an In ^III Amidinate and H ₂ O Kim, Sang Bok; Jayaraman, Ashwin; Chua, Danny Chemistry - A European Journal, Vol. 24, Issue 38 https://doi.org/10.1002/chem.201802317	journal	June 2018
Exploring Bio-inspired Quinone-Based Organic Redox Flow Batteries: A Combined Experimental and Computational Study Ding, Yu; Li, Yafei; Yu, Guihua Chem, Vol. 1, Issue 5 https://doi.org/10.1016/j.chempr.2016.09.004	journal	November 2016
Designer Two-Electron Storage Viologen Anolyte Materials for Neutral Aqueous Organic Redox Flow Batteries DeBruler, Camden; Hu, Bo; Moss, Jared Chem, Vol. 3, Issue 6 https://doi.org/10.1016/j.chempr.2017.11.001	journal	December 2017
Progress and prospects of next-generation redox flow batteries Zhang, Changkun; Zhang, Leyuan; Ding, Yu Energy Storage Materials, Vol. 15 https://doi.org/10.1016/j.ensm.2018.06.008	journal	November 2018
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
Alkaline Quinone Flow Battery with Long Lifetime at pH 12 Kwabi, David G.; Lin, Kaixiang; Ji, Yunlong Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.07.005	journal	September 2018
Alkaline Quinone Flow Battery with Long Lifetime at pH 12 Kwabi, David G.; Lin, Kaixiang; Ji, Yunlong Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.08.013	journal	September 2018
Unraveling pH dependent cycling stability of ferricyanide/ferrocyanide in redox flow batteries Luo, Jian; Sam, Alyssa; Hu, Bo Nano Energy, Vol. 42 https://doi.org/10.1016/j.nanoen.2017.10.057	journal	December 2017
TEMPO/Phenazine Combi-Molecule: A Redox-Active Material for Symmetric Aqueous Redox-Flow Batteries Winsberg, Jan; Stolze, Christian; Muench, Simon ACS Energy Letters, Vol. 1, Issue 5 https://doi.org/10.1021/acsenergylett.6b00413	journal	October 2016
Aqueous 2,2,6,6-Tetramethylpiperidine- N -oxyl Catholytes for a High-Capacity and High Current Density Oxygen-Insensitive Hybrid-Flow Battery Winsberg, Jan; Stolze, Christian; Schwenke, Almut ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00655	journal	January 2017
A Neutral pH Aqueous Organic–Organometallic Redox Flow Battery with Extremely High Capacity Retention Beh, Eugene S.; De Porcellinis, Diana; Gracia, Rebecca L. ACS Energy Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsenergylett.7b00019	journal	February 2017
A Sulfonate-Functionalized Viologen Enabling Neutral Cation Exchange, Aqueous Organic Redox Flow Batteries toward Renewable Energy Storage DeBruler, Camden; Hu, Bo; Moss, Jared ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.7b01302	journal	February 2018
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
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
Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage Hu, Bo; DeBruler, Camden; Rhodes, Zayn Journal of the American Chemical Society, Vol. 139, Issue 3 https://doi.org/10.1021/jacs.6b10984	journal	January 2017
Physical Organic Approach to Persistent, Cyclable, Low-Potential Electrolytes for Flow Battery Applications Sevov, Christo S.; Hickey, David P.; Cook, Monique E. Journal of the American Chemical Society, Vol. 139, Issue 8 https://doi.org/10.1021/jacs.7b00147	journal	February 2017
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
An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials Janoschka, Tobias; Martin, Norbert; Martin, Udo Nature, Vol. 534, Issue 7607 https://doi.org/10.1038/nature18909	journal	June 2016
A biomimetic redox flow battery based on flavin mononucleotide Orita, Akihiro; Verde, Michael G.; Sakai, Masanori Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13230	journal	October 2016
A redox-flow battery with an alloxazine-based organic electrolyte Lin, Kaixiang; Gómez-Bombarelli, Rafael; Beh, Eugene S. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.102	journal	July 2016
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
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
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
Synthesis and characterization of TEMPO- and viologen-polymers for water-based redox-flow batteries Janoschka, T.; Morgenstern, S.; Hiller, H. Polymer Chemistry, Vol. 6, Issue 45 https://doi.org/10.1039/C5PY01602A	journal	January 2015
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
Estimating the cost of organic battery active materials: a case study on anthraquinone disulfonic acid Dieterich, Vincent; Milshtein, Jarrod D.; Barton, John L. Translational Materials Research, Vol. 5, Issue 3 https://doi.org/10.1088/2053-1613/aacb0e	journal	July 2018
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
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
The irreversible momentum of clean energy Obama, Barack Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aam6284	journal	January 2017
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
Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods Goulet, Marc-Antoni; Aziz, Michael J. Journal of The Electrochemical Society, Vol. 165, Issue 7 https://doi.org/10.1149/2.0891807jes	journal	January 2018
An Inexpensive Aqueous Flow Battery for Large-Scale Electrical Energy Storage Based on Water-Soluble Organic Redox Couples Yang, Bo; Hoober-Burkhardt, Lena; Wang, Fang Journal of The Electrochemical Society, Vol. 161, Issue 9 https://doi.org/10.1149/2.1001409jes	journal	January 2014
High-Performance Aqueous Organic Flow Battery with Quinone-Based Redox Couples at Both Electrodes Yang, Bo; Hoober-Burkhardt, Lena; Krishnamoorthy, Sankarganesh Journal of The Electrochemical Society, Vol. 163, Issue 7 https://doi.org/10.1149/2.1371607jes	journal	January 2016
Flow Batteries Nguyen, Trung; Savinell, Robert F. The Electrochemical Society Interface, Vol. 19, Issue 3 https://doi.org/10.1149/2.F06103if	journal	January 2010
Comparison of Capacity Retention Rates During Cycling of Quinone-Bromide Flow Batteries Gerhardt, Michael R.; Beh, Eugene S.; Tong, Liuchuan MRS Advances, Vol. 2, Issue 8 https://doi.org/10.1557/adv.2016.667	journal	December 2016

Cited By (8)

A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte Hu, Bo; Luo, Jian; Hu, Maowei Angewandte Chemie, Vol. 131, Issue 46 https://doi.org/10.1002/ange.201907934	journal	September 2019
A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte Hu, Bo; Luo, Jian; Hu, Maowei Angewandte Chemie International Edition, Vol. 58, Issue 46 https://doi.org/10.1002/anie.201907934	journal	November 2019
In situ NMR metrology reveals reaction mechanisms in redox flow batteries Zhao, Evan Wenbo; Liu, Tao; Jónsson, Erlendur Nature, Vol. 579, Issue 7798 https://doi.org/10.1038/s41586-020-2081-7	journal	March 2020
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
Efficient electrochemical synthesis of robust, densely functionalized water soluble quinones Gerken, James B.; Stamoulis, Alexios; Suh, Sung-Eun Chemical Communications, Vol. 56, Issue 8 https://doi.org/10.1039/c9cc08878d	journal	January 2020
Mapping the frontiers of quinone stability in aqueous media: implications for organic aqueous redox flow batteries Tabor, Daniel P.; Gómez-Bombarelli, Rafael; Tong, Liuchuan Journal of Materials Chemistry A, Vol. 7, Issue 20 https://doi.org/10.1039/c9ta03219c	journal	January 2019
Structure reorganization-controlled electron transfer of bipyridine derivatives as organic redox couples Lv, Yang; Liu, Yiyang; Feng, Ting Journal of Materials Chemistry A, Vol. 7, Issue 47 https://doi.org/10.1039/c9ta08910a	journal	January 2019
Investigating the Effects of Primary Amine Linkers with Different Carbon Chain Lengths on the Acid Dissociation Constant (p K a) for Covalently Immobilized Anthraquinone at the Electrode Surface Using Linear and Non-Linear Fittings Hamzah, Hairul Hisham; Chein, Wee Chew; Rahiman, Siti Sarah Fazalul Journal of The Electrochemical Society, Vol. 166, Issue 16 https://doi.org/10.1149/2.0301916jes	journal	January 2019

Similar Records

A Water-Miscible Quinone Flow Battery with High Volumetric Capacity and Energy Density

Journal Article · Tue May 21 20:00:00 EDT 2019 · ACS Energy Letters · OSTI ID:1597276

Highly Stable, Low Redox Potential Quinone for Aqueous Flow Batteries**

Journal Article · Wed Feb 23 19:00:00 EST 2022 · Batteries & Supercaps · OSTI ID:1846349

Related Subjects

25 ENERGY STORAGE
energy storage
long lifetime
quinone
redox‐flow batteries

A Phosphonate-Functionalized Quinone Redox Flow Battery at Near-Neutral pH with Record Capacity Retention Rate

Citation Formats

References (44)

Cited By (8)

Similar Records

Related Subjects