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Title: Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries

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:
 [1] ;  [2] ;  [2] ;  [2] ;  [3] ;  [3] ;  [4] ;  [2] ;  [3] ; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of Illinois, Urbana, IL (United States)
  4. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
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
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOD
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
OSTI Identifier:
1379650

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., 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. 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., and Helms, Brett A.. 2017. "Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries". United States. doi: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 = {2017},
month = {1}
}

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