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Title: 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 » 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.« less

Authors:
 [1];  [2];  [3];  [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  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
  2. 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
  3. 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 Lab. (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. doi: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. doi: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 = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1021/acscentsci.7b00544

Citation Metrics:
Cited by: 12 works
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Figures / Tables:

Figure 1 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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Iodine(III)-Mediated Electrochemical Trifluoroethoxylactonisation: Rational Reaction Optimisation and Prediction of Mediator Activity
journal, October 2018

  • Möckel, Robert; Babaoglu, Emre; Hilt, Gerhard
  • Chemistry - A European Journal, Vol. 24, Issue 59
  • DOI: 10.1002/chem.201804152

Organic Functionalization of Polyoxovanadate–Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries
journal, November 2018

  • VanGelder, Lauren E.; Petel, Brittney E.; Nachtigall, Olaf
  • ChemSusChem, Vol. 11, Issue 23
  • DOI: 10.1002/cssc.201802029

Crossover in Membranes for Aqueous Soluble Organic Redox Flow Batteries
journal, January 2019

  • Small, Leo J.; Pratt, Harry D.; Anderson, Travis M.
  • Journal of The Electrochemical Society, Vol. 166, Issue 12
  • DOI: 10.1149/2.0681912jes

Gradient-Distributed Metal-Organic Framework-Based Porous Membranes for Nonaqueous Redox Flow Batteries
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  • Peng, Sangshan; Zhang, Leyuan; Zhang, Changkun
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  • DOI: 10.1002/aenm.201802533

Crosslinked colloids with cyclopropenium cations
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  • Brucks, Spencer D.; Steinman, Noam Y.; Starr, Rachel L.
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Pyridyl group design in viologens for anolyte materials in organic redox flow batteries
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  • Chen, Chen; Zhang, Shun; Zhu, Yingzhong
  • RSC Advances, Vol. 8, Issue 34
  • DOI: 10.1039/c8ra02641f

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
  • DOI: 10.1039/c8ta03312a

Physicochemical implications of alkoxide “mixing” in polyoxovanadium clusters for nonaqueous energy storage
journal, January 2019

  • VanGelder, Lauren E.; Schreiber, Eric; Matson, Ellen M.
  • Journal of Materials Chemistry A, Vol. 7, Issue 9
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Asymmetric allyl-activation of organosulfides for high-energy reversible redox flow batteries
journal, January 2019

  • Weng, Guo-Ming; Yang, Bin; Liu, Chi-You
  • Energy & Environmental Science, Vol. 12, Issue 7
  • DOI: 10.1039/c9ee00336c

Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries
journal, March 2019


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