High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
Abstract
Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairingmore »
- Authors:
-
[3];
[2];
[2];
[1]
- Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States, Joint Center for Energy Storage Research (JCESR), 9700 S. Cass Avenue, Argonne, Illinois 60439, United States
- Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States, Joint Center for Energy Storage Research (JCESR), 9700 S. Cass Avenue, Argonne, Illinois 60439, United States
- The Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States, Joint Center for Energy Storage Research (JCESR), 9700 S. Cass Avenue, Argonne, Illinois 60439, United States
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1417219
- Alternate Identifier(s):
- OSTI ID: 1433121; OSTI ID: 1508601
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 4 Journal Issue: 2; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE
Citation Formats
Hendriks, Koen H., Robinson, Sophia G., Braten, Miles N., Sevov, Christo S., Helms, Brett A., Sigman, Matthew S., Minteer, Shelley D., and Sanford, Melanie S. High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries. United States: N. p., 2018.
Web. doi:10.1021/acscentsci.7b00544.
Hendriks, Koen H., Robinson, Sophia G., Braten, Miles N., Sevov, Christo S., Helms, Brett A., Sigman, Matthew S., Minteer, Shelley D., & Sanford, Melanie S. High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries. United States. https://doi.org/10.1021/acscentsci.7b00544
Hendriks, Koen H., Robinson, Sophia G., Braten, Miles N., Sevov, Christo S., Helms, Brett A., Sigman, Matthew S., Minteer, Shelley D., and Sanford, Melanie S. Wed .
"High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries". United States. https://doi.org/10.1021/acscentsci.7b00544.
@article{osti_1417219,
title = {High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries},
author = {Hendriks, Koen H. and Robinson, Sophia G. and Braten, Miles N. and Sevov, Christo S. and Helms, Brett A. and Sigman, Matthew S. and Minteer, Shelley D. and Sanford, Melanie S.},
abstractNote = {Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.},
doi = {10.1021/acscentsci.7b00544},
journal = {ACS Central Science},
number = 2,
volume = 4,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2018},
month = {Wed Jan 17 00:00:00 EST 2018}
}
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https://doi.org/10.1021/acscentsci.7b00544
https://doi.org/10.1021/acscentsci.7b00544
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Cited by: 98 works
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Figures / Tables:
Figure 1: Schematic representation of the operation of a microporous membrane in a flow battery using redox-active oligomers.
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Works referencing / citing this record:
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