Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries
Abstract
Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm-2 day-1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.
- Authors:
-
[2]
- Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Illinois, Urbana, IL (United States)
- Univ. of Michigan, Ann Arbor, MI (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOD
- OSTI Identifier:
- 1379650
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 6; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; energy storage; macromolecular chemistry; membranes; polymers; redox-flow batteries
Citation Formats
Doris, Sean E., Ward, Ashleigh L., Baskin, Artem, Frischmann, Peter D., Gavvalapalli, Nagarjuna, Chénard, Etienne, Sevov, Christo S., Prendergast, David, Moore, Jeffrey S., and Helms, Brett A. Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries. United States: N. p., 2017.
Web. doi:10.1002/anie.201610582.
Doris, Sean E., Ward, Ashleigh L., Baskin, Artem, Frischmann, Peter D., Gavvalapalli, Nagarjuna, Chénard, Etienne, Sevov, Christo S., Prendergast, David, Moore, Jeffrey S., & Helms, Brett A. Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries. United States. https://doi.org/10.1002/anie.201610582
Doris, Sean E., Ward, Ashleigh L., Baskin, Artem, Frischmann, Peter D., Gavvalapalli, Nagarjuna, Chénard, Etienne, Sevov, Christo S., Prendergast, David, Moore, Jeffrey S., and Helms, Brett A. Tue .
"Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries". United States. https://doi.org/10.1002/anie.201610582. https://www.osti.gov/servlets/purl/1379650.
@article{osti_1379650,
title = {Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries},
author = {Doris, Sean E. and Ward, Ashleigh L. and Baskin, Artem and Frischmann, Peter D. and Gavvalapalli, Nagarjuna and Chénard, Etienne and Sevov, Christo S. and Prendergast, David and Moore, Jeffrey S. and Helms, Brett A.},
abstractNote = {Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. In this paper, we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm-2 day-1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. Finally, this strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.},
doi = {10.1002/anie.201610582},
journal = {Angewandte Chemie (International Edition)},
number = 6,
volume = 56,
place = {United States},
year = {Tue Jan 10 00:00:00 EST 2017},
month = {Tue Jan 10 00:00:00 EST 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 90 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Molecular Separation with Organic Solvent Nanofiltration: A Critical Review
journal, October 2014
- Marchetti, Patrizia; Jimenez Solomon, Maria F.; Szekely, Gyorgy
- Chemical Reviews, Vol. 114, Issue 21
Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries
journal, January 2014
- Darling, Robert M.; Gallagher, Kevin G.; Kowalski, Jeffrey A.
- Energy & Environmental Science, Vol. 7, Issue 11, p. 3459-3477
Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage
journal, January 2006
- McKeown, Neil B.; Budd, Peter M.
- Chemical Society Reviews, Vol. 35, Issue 8, p. 675-683
Exploitation of Intrinsic Microporosity in Polymer-Based Materials
journal, June 2010
- McKeown, Neil B.; Budd, Peter M.
- Macromolecules, Vol. 43, Issue 12
Gas Separation, Free Volume Distribution, and Physical Aging of a Highly Microporous Spirobisindane Polymer
journal, April 2008
- Staiger, Chad L.; Pas, Steven J.; Hill, Anita J.
- Chemistry of Materials, Vol. 20, Issue 8
An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials
journal, October 2015
- Janoschka, Tobias; Martin, Norbert; Martin, Udo
- Nature, Vol. 527, Issue 7576, p. 78-81
Understanding and controlling the chemical evolution and polysulfide-blocking ability of lithium–sulfur battery membranes cast from polymers of intrinsic microporosity
journal, January 2016
- Doris, Sean E.; Ward, Ashleigh L.; Frischmann, Peter D.
- Journal of Materials Chemistry A, Vol. 4, Issue 43
Azide-based Cross-Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation
journal, March 2011
- Du, Naiying; Cin, Mauro M. Dal-; Pinnau, Ingo
- Macromolecular Rapid Communications, Vol. 32, Issue 8
Battery Separators
journal, October 2004
- Arora, Pankaj; Zhang, Zhengming (John)
- Chemical Reviews, Vol. 104, Issue 10
Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials
journal, January 2004
- Budd, Peter M.; Ghanem, Bader S.; Makhseed, Saad
- Chemical Communications, Issue 2
Recent Progress in Redox Flow Battery Research and Development
journal, September 2012
- Wang, Wei; Luo, Qingtao; Li, Bin
- Advanced Functional Materials, Vol. 23, Issue 8, p. 970-986
The Chemistry of Redox-Flow Batteries
journal, June 2015
- Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana
- Angewandte Chemie International Edition, Vol. 54, Issue 34
Redox Active Colloids as Discrete Energy Storage Carriers
journal, September 2016
- Montoto, Elena C.; Nagarjuna, Gavvalapalli; Hui, Jingshu
- Journal of the American Chemical Society, Vol. 138, Issue 40
A review of current developments in non-aqueous redox flow batteries: characterization of their membranes for design perspective
journal, January 2013
- Shin, Sung-Hee; Yun, Sung-Hyun; Moon, Seung-Hyeon
- RSC Advances, Vol. 3, Issue 24, p. 9095-9116
Inorganic solid Li ion conductors: An overview
journal, June 2009
- Knauth, Philippe
- Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916
Transport Property Requirements for Flow Battery Separators
journal, July 2015
- Darling, Robert; Gallagher, Kevin; Xie, Wei
- Journal of The Electrochemical Society, Vol. 163, Issue 1
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery
journal, April 2015
- Wei, Xiaoliang; Xu, Wu; Huang, Jinhua
- Angewandte Chemie, Vol. 127, Issue 30
A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR
journal, January 2016
- Duan, Wentao; Vemuri, Rama S.; Milshtein, Jarrod D.
- Journal of Materials Chemistry A, Vol. 4, Issue 15
Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries
journal, November 2014
- Huang, Jinhua; Cheng, Lei; Assary, Rajeev S.
- Advanced Energy Materials, Vol. 5, Issue 6
Evolutionary Design of Low Molecular Weight Organic Anolyte Materials for Applications in Nonaqueous Redox Flow Batteries
journal, October 2015
- Sevov, Christo S.; Brooner, Rachel E. M.; Chénard, Etienne
- Journal of the American Chemical Society, Vol. 137, Issue 45
Impact of Redox-Active Polymer Molecular Weight on the Electrochemical Properties and Transport Across Porous Separators in Nonaqueous Solvents
journal, October 2014
- Nagarjuna, Gavvalapalli; Hui, Jingshu; Cheng, Kevin J.
- Journal of the American Chemical Society, Vol. 136, Issue 46, p. 16309-16316
Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen Redox Active Polymers
journal, October 2016
- Burgess, Mark; Chénard, Etienne; Hernández-Burgos, Kenneth
- Chemistry of Materials, Vol. 28, Issue 20
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Die Chemie der Redox-Flow-Batterien
journal, June 2015
- Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana
- Angewandte Chemie, Vol. 127, Issue 34
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries
journal, August 2015
- Li, Changyi; Ward, Ashleigh L.; Doris, Sean E.
- Nano Letters, Vol. 15, Issue 9
Redox Active Polymers as Soluble Nanomaterials for Energy Storage
journal, September 2016
- Burgess, Mark; Moore, Jeffrey S.; Rodríguez-López, Joaquín
- Accounts of Chemical Research, Vol. 49, Issue 11
An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery
journal, June 2012
- Brushett, Fikile R.; Vaughey, John T.; Jansen, Andrew N.
- Advanced Energy Materials, Vol. 2, Issue 11, p. 1390-1396
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery
journal, April 2015
- Wei, Xiaoliang; Xu, Wu; Huang, Jinhua
- Angewandte Chemie International Edition, Vol. 54, Issue 30
Poly(boron-dipyrromethene)—A Redox-Active Polymer Class for Polymer Redox-Flow Batteries
journal, May 2016
- Winsberg, Jan; Hagemann, Tino; Muench, Simon
- Chemistry of Materials, Vol. 28, Issue 10
Battery Separators
journal, December 2004
- Arora, Pankaj; Zhang, Zhengming
- ChemInform, Vol. 35, Issue 50
Polymers of Intrinsic Microporosity (PIMs): Organic Materials for Membrane Separations, Heterogeneous Catalysis and Hydrogen Storage
journal, November 2006
- McKeown, Neil B.; Budd, Peter M.
- ChemInform, Vol. 37, Issue 45
An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials
journal, June 2016
- Janoschka, Tobias; Martin, Norbert; Martin, Udo
- Nature, Vol. 534, Issue 7607
Works referencing / citing this record:
Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies
journal, January 2018
- Li, Changyi; Meckler, Stephen M.; Smith, Zachary P.
- Advanced Materials, Vol. 30, Issue 8
Gradient-Distributed Metal-Organic Framework-Based Porous Membranes for Nonaqueous Redox Flow Batteries
journal, October 2018
- Peng, Sangshan; Zhang, Leyuan; Zhang, Changkun
- Advanced Energy Materials, Vol. 8, Issue 33
Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage
journal, February 2018
- Ma, Ting; Pan, Zeng; Miao, Licheng
- Angewandte Chemie, Vol. 130, Issue 12
Strategien für kostengünstige und leistungsstarke Dual‐Ionen‐Batterien
journal, November 2019
- Zhou, Xiaolong; Liu, Qirong; Jiang, Chunlei
- Angewandte Chemie, Vol. 132, Issue 10
A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte
journal, September 2019
- Hu, Bo; Luo, Jian; Hu, Maowei
- Angewandte Chemie, Vol. 131, Issue 46
Strategies towards Low‐Cost Dual‐Ion Batteries with High Performance
journal, November 2019
- Zhou, Xiaolong; Liu, Qirong; Jiang, Chunlei
- Angewandte Chemie International Edition, Vol. 59, Issue 10
A pH‐Neutral, Metal‐Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte
journal, November 2019
- Hu, Bo; Luo, Jian; Hu, Maowei
- Angewandte Chemie International Edition, Vol. 58, Issue 46
Toward High‐Voltage, Energy‐Dense, and Durable Aqueous Organic Redox Flow Batteries: Role of the Supporting Electrolytes
journal, September 2018
- Chen, Ruiyong
- ChemElectroChem, Vol. 6, Issue 3
Polymers of Intrinsic Microporosity in Triphasic Electrochemistry: Perspectives
journal, July 2019
- Marken, Frank; Madrid, Elena; Zhao, Yuanzhu
- ChemElectroChem, Vol. 6, Issue 17
Electrochemical Evaluation of a Napthalene Diimide Derivative for Potential Application in Aqueous Organic Redox Flow Batteries
journal, August 2019
- Wiberg, Cedrik; Owusu, Francis; Wang, Ergang
- Energy Technology, Vol. 7, Issue 11
Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries
journal, January 2018
- VanGelder, L. E.; Kosswattaarachchi, A. M.; Forrestel, P. L.
- Chemical Science, Vol. 9, Issue 6
Anion–π interactions in lithium–organic redox flow batteries
journal, January 2019
- Li, Lei; Hong, Yu-Jian; Chen, Dong-Yang
- Chemical Communications, Vol. 55, Issue 16
Heterometal functionalization yields improved energy density for charge carriers in nonaqueous redox flow batteries
journal, January 2018
- VanGelder, Lauren E.; Matson, Ellen M.
- Journal of Materials Chemistry A, Vol. 6, Issue 28
Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries
journal, March 2019
- VanGelder, Lauren E.; Cook, Timothy R.; Matson, Ellen M.
- Comments on Inorganic Chemistry, Vol. 39, Issue 2
Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage
journal, February 2018
- Ma, Ting; Pan, Zeng; Miao, Licheng
- Angewandte Chemie International Edition, Vol. 57, Issue 12
High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
journal, January 2018
- Hendriks, Koen H.; Robinson, Sophia G.; Braten, Miles N.
- ACS Central Science, Vol. 4, Issue 2
Preventing Crossover in Redox Flow Batteries through Active Material Oligomerization
journal, February 2018
- Odom, Susan
- ACS Central Science, Vol. 4, Issue 2