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High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries

[Image: see text] 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)...

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Autores principales: Hendriks, Koen H., Robinson, Sophia G., Braten, Miles N., Sevov, Christo S., Helms, Brett A., Sigman, Matthew S., Minteer, Shelley D., Sanford, Melanie S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5833001/
https://www.ncbi.nlm.nih.gov/pubmed/29532018
http://dx.doi.org/10.1021/acscentsci.7b00544
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author Hendriks, Koen H.
Robinson, Sophia G.
Braten, Miles N.
Sevov, Christo S.
Helms, Brett A.
Sigman, Matthew S.
Minteer, Shelley D.
Sanford, Melanie S.
author_facet Hendriks, Koen H.
Robinson, Sophia G.
Braten, Miles N.
Sevov, Christo S.
Helms, Brett A.
Sigman, Matthew S.
Minteer, Shelley D.
Sanford, Melanie S.
author_sort Hendriks, Koen H.
collection PubMed
description [Image: see text] 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.
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spelling pubmed-58330012018-03-12 High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries Hendriks, Koen H. Robinson, Sophia G. Braten, Miles N. Sevov, Christo S. Helms, Brett A. Sigman, Matthew S. Minteer, Shelley D. Sanford, Melanie S. ACS Cent Sci [Image: see text] 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. American Chemical Society 2018-01-17 2018-02-28 /pmc/articles/PMC5833001/ /pubmed/29532018 http://dx.doi.org/10.1021/acscentsci.7b00544 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle 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
title High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
title_full High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
title_fullStr High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
title_full_unstemmed High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
title_short High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries
title_sort high-performance oligomeric catholytes for effective macromolecular separation in nonaqueous redox flow batteries
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5833001/
https://www.ncbi.nlm.nih.gov/pubmed/29532018
http://dx.doi.org/10.1021/acscentsci.7b00544
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