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Title: Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices

Abstract

Here, we lay the design rules for linking microporous polymer membrane architecture and pore chemistry to membrane stability, conductivity, and transport selectivity in aqueous electrolytes over a broad range of pH. We tie these attributes to prospects for crossover-free electrochemical cell operation. These guiding principles are applied to two emerging cell chemistries for grid batteries: specifically, Zn–TEMPO-4-sulfate and Zn–K4Fe(CN)6 cells. Key to our success is the placement of ionizable amidoxime functionalities, which are stable at high pH, within the pores of microporous ladder polymer membranes, yielding a family of charge-neutral and cation exchange membranes at low and high pH, respectively—which we call AquaPIMs. Their notably high conductivity (up to 21.5 mS cm-1 in 5.0 M aqueous KOH) and high transport selectivity (up to 104 reduction in active-material permeability through the membrane) suggest exciting opportunities for battery development, even beyond those presently demonstrated.The energy efficiency and cycle life of electrochemical cells with dissolved active materials are inextricably tied to the stability, conductivity, and transport selectivity of the cell's membrane. Membrane design rules have been lacking for such cells operating under harsh conditions, such as high alkalinity, due to the lack of selective, stable membranes. Here, we examined several classes of membranesmore » for three aqueous Zn-based cell chemistries. In doing so, we uncovered a simple relationship between the membrane selectivity and the cell's cycle life, such that it is now possible to predict the lifetime of the cell on the basis of its membrane properties, thus avoiding time- or resource-intensive experimentation in large-format cells. Our work should greatly accelerate the identification of membranes for long-lasting, MW-scale redox-flow, and other low-cost grid batteries, which are required to last 10–20 years.« less

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1570013
Alternate Identifier(s):
OSTI ID: 1631613
Grant/Contract Number:  
AC02-05CH11231; SC0001015
Resource Type:
Published Article
Journal Name:
Joule
Additional Journal Information:
Journal Name: Joule Journal Volume: 3 Journal Issue: 12; Journal ID: ISSN 2542-4351
Publisher:
Elsevier - Cell Press
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; polymers of intrinsic microporosity; membrane; cation exchange membrane; zinc battery; grid-scale energy storage; alkaline battery

Citation Formats

Baran, Miranda J., Braten, Miles N., Sahu, Swagat, Baskin, Artem, Meckler, Stephen M., Li, Longjun, Maserati, Lorenzo, Carrington, Mark E., Chiang, Yet-Ming, Prendergast, David, and Helms, Brett A. Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices. United States: N. p., 2019. Web. doi:10.1016/j.joule.2019.08.025.
Baran, Miranda J., Braten, Miles N., Sahu, Swagat, Baskin, Artem, Meckler, Stephen M., Li, Longjun, Maserati, Lorenzo, Carrington, Mark E., Chiang, Yet-Ming, Prendergast, David, & Helms, Brett A. Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices. United States. doi:https://doi.org/10.1016/j.joule.2019.08.025
Baran, Miranda J., Braten, Miles N., Sahu, Swagat, Baskin, Artem, Meckler, Stephen M., Li, Longjun, Maserati, Lorenzo, Carrington, Mark E., Chiang, Yet-Ming, Prendergast, David, and Helms, Brett A. Sun . "Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices". United States. doi:https://doi.org/10.1016/j.joule.2019.08.025.
@article{osti_1570013,
title = {Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices},
author = {Baran, Miranda J. and Braten, Miles N. and Sahu, Swagat and Baskin, Artem and Meckler, Stephen M. and Li, Longjun and Maserati, Lorenzo and Carrington, Mark E. and Chiang, Yet-Ming and Prendergast, David and Helms, Brett A.},
abstractNote = {Here, we lay the design rules for linking microporous polymer membrane architecture and pore chemistry to membrane stability, conductivity, and transport selectivity in aqueous electrolytes over a broad range of pH. We tie these attributes to prospects for crossover-free electrochemical cell operation. These guiding principles are applied to two emerging cell chemistries for grid batteries: specifically, Zn–TEMPO-4-sulfate and Zn–K4Fe(CN)6 cells. Key to our success is the placement of ionizable amidoxime functionalities, which are stable at high pH, within the pores of microporous ladder polymer membranes, yielding a family of charge-neutral and cation exchange membranes at low and high pH, respectively—which we call AquaPIMs. Their notably high conductivity (up to 21.5 mS cm-1 in 5.0 M aqueous KOH) and high transport selectivity (up to 104 reduction in active-material permeability through the membrane) suggest exciting opportunities for battery development, even beyond those presently demonstrated.The energy efficiency and cycle life of electrochemical cells with dissolved active materials are inextricably tied to the stability, conductivity, and transport selectivity of the cell's membrane. Membrane design rules have been lacking for such cells operating under harsh conditions, such as high alkalinity, due to the lack of selective, stable membranes. Here, we examined several classes of membranes for three aqueous Zn-based cell chemistries. In doing so, we uncovered a simple relationship between the membrane selectivity and the cell's cycle life, such that it is now possible to predict the lifetime of the cell on the basis of its membrane properties, thus avoiding time- or resource-intensive experimentation in large-format cells. Our work should greatly accelerate the identification of membranes for long-lasting, MW-scale redox-flow, and other low-cost grid batteries, which are required to last 10–20 years.},
doi = {10.1016/j.joule.2019.08.025},
journal = {Joule},
number = 12,
volume = 3,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
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DOI: https://doi.org/10.1016/j.joule.2019.08.025

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