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Title: Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage

Abstract

Membranes with fast and selective ion transport are widely used for water purification and devices for energy conversion and storage including fuel cells, redox flow batteries and electrochemical reactors. However, it remains challenging to design cost-effective, easily processed ion-conductive membranes with well-defined pore architectures. Here in this paper, we report a new approach to designing membranes with narrow molecular-sized channels and hydrophilic functionality that enable fast transport of salt ions and high size-exclusion selectivity towards small organic molecules. These membranes, based on polymers of intrinsic microporosity containing Tröger’s base or amidoxime groups, demonstrate that exquisite control over subnanometre pore structure, the introduction of hydrophilic functional groups and thickness control all play important roles in achieving fast ion transport combined with high molecular selectivity. These membranes enable aqueous organic flow batteries with high energy efficiency and high capacity retention, suggesting their utility for a variety of energy-related devices and water purification processes.

Authors:
 [1]; ORCiD logo [1];  [2];  [2];  [3];  [4];  [2];  [1];  [1];  [1]; ORCiD logo [5]; ORCiD logo [5];  [6]; ORCiD logo [6];  [7];  [5];  [6];  [5];  [3]; ORCiD logo [2] more »; ORCiD logo [1] « less
  1. Imperial College London, London (United Kingdom). Barrer Centre
  2. Univ. of Edinburgh, Scotland (United Kingdom)
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. of Cambridge (United Kingdom); Tongji Univ., Shanghai (China). Shanghai Key Lab. of Chemical Assessment and Sustainability, Dept. of Chemistry
  5. Imperial College London, London (United Kingdom)
  6. Univ. of Liverpool (United Kingdom). Leverhulme Research Centre for Functional Materials Design
  7. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States). X-ray Science Division, Joint Center for Energy Storage Research (JCESR)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Engineering and Physical Sciences Research Council (EPSRC); European Union (EU) - Horizon 2020 Research and Innovation Programme; European Research Council (ERC); Imperial College London; China Scholarship Council; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1616156
Grant/Contract Number:  
AC02-06CH11357; 608490; 758370
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 19; Journal Issue: 2; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Tan, Rui, Wang, Anqi, Malpass-Evans, Richard, Williams, Rhodri, Zhao, Evan Wenbo, Liu, Tao, Ye, Chunchun, Zhou, Xiaoqun, Darwich, Barbara Primera, Fan, Zhiyu, Turcani, Lukas, Jackson, Edward, Chen, Linjiang, Chong, Samantha Y., Li, Tao, Jelfs, Kim E., Cooper, Andrew I., Brandon, Nigel P., Grey, Clare P., McKeown, Neil B., and Song, Qilei. Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage. United States: N. p., 2019. Web. doi:10.1038/s41563-019-0536-8.
Tan, Rui, Wang, Anqi, Malpass-Evans, Richard, Williams, Rhodri, Zhao, Evan Wenbo, Liu, Tao, Ye, Chunchun, Zhou, Xiaoqun, Darwich, Barbara Primera, Fan, Zhiyu, Turcani, Lukas, Jackson, Edward, Chen, Linjiang, Chong, Samantha Y., Li, Tao, Jelfs, Kim E., Cooper, Andrew I., Brandon, Nigel P., Grey, Clare P., McKeown, Neil B., & Song, Qilei. Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage. United States. doi:https://doi.org/10.1038/s41563-019-0536-8
Tan, Rui, Wang, Anqi, Malpass-Evans, Richard, Williams, Rhodri, Zhao, Evan Wenbo, Liu, Tao, Ye, Chunchun, Zhou, Xiaoqun, Darwich, Barbara Primera, Fan, Zhiyu, Turcani, Lukas, Jackson, Edward, Chen, Linjiang, Chong, Samantha Y., Li, Tao, Jelfs, Kim E., Cooper, Andrew I., Brandon, Nigel P., Grey, Clare P., McKeown, Neil B., and Song, Qilei. Mon . "Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage". United States. doi:https://doi.org/10.1038/s41563-019-0536-8. https://www.osti.gov/servlets/purl/1616156.
@article{osti_1616156,
title = {Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage},
author = {Tan, Rui and Wang, Anqi and Malpass-Evans, Richard and Williams, Rhodri and Zhao, Evan Wenbo and Liu, Tao and Ye, Chunchun and Zhou, Xiaoqun and Darwich, Barbara Primera and Fan, Zhiyu and Turcani, Lukas and Jackson, Edward and Chen, Linjiang and Chong, Samantha Y. and Li, Tao and Jelfs, Kim E. and Cooper, Andrew I. and Brandon, Nigel P. and Grey, Clare P. and McKeown, Neil B. and Song, Qilei},
abstractNote = {Membranes with fast and selective ion transport are widely used for water purification and devices for energy conversion and storage including fuel cells, redox flow batteries and electrochemical reactors. However, it remains challenging to design cost-effective, easily processed ion-conductive membranes with well-defined pore architectures. Here in this paper, we report a new approach to designing membranes with narrow molecular-sized channels and hydrophilic functionality that enable fast transport of salt ions and high size-exclusion selectivity towards small organic molecules. These membranes, based on polymers of intrinsic microporosity containing Tröger’s base or amidoxime groups, demonstrate that exquisite control over subnanometre pore structure, the introduction of hydrophilic functional groups and thickness control all play important roles in achieving fast ion transport combined with high molecular selectivity. These membranes enable aqueous organic flow batteries with high energy efficiency and high capacity retention, suggesting their utility for a variety of energy-related devices and water purification processes.},
doi = {10.1038/s41563-019-0536-8},
journal = {Nature Materials},
number = 2,
volume = 19,
place = {United States},
year = {2019},
month = {12}
}

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Works referenced in this record:

Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries
journal, January 2014

  • Darling, Robert M.; Gallagher, Kevin G.; Kowalski, Jeffrey A.
  • Energy & Environmental Science, Vol. 7, Issue 11, p. 3459-3477
  • DOI: 10.1039/C4EE02158D

Zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes for gas separation
journal, January 2012

  • Song, Qilei; Nataraj, S. K.; Roussenova, Mina V.
  • Energy & Environmental Science, Vol. 5, Issue 8
  • DOI: 10.1039/c2ee21996d

An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials
journal, October 2015

  • Janoschka, Tobias; Martin, Norbert; Martin, Udo
  • Nature, Vol. 527, Issue 7576, p. 78-81
  • DOI: 10.1038/nature15746

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

  • Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
  • Nature, Vol. 508, Issue 7497
  • DOI: 10.1038/nature13249

An operationally flexible fuel cell based on quaternary ammonium-biphosphate ion pairs
journal, August 2016

  • Lee, Kwan-Soo; Spendelow, Jacob S.; Choe, Yoong-Kee
  • Nature Energy, Vol. 1, Issue 9, Article No. 16120
  • DOI: 10.1038/nenergy.2016.120

Pure- and mixed-gas CO2/CH4 separation properties of PIM-1 and an amidoxime-functionalized PIM-1
journal, May 2014


Acidity of the Amidoxime Functional Group in Aqueous Solution: A Combined Experimental and Computational Study
journal, February 2015

  • Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 8
  • DOI: 10.1021/jp512778x

Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO2 capture
journal, January 2012

  • Patel, Hasmukh A.; Yavuz, Cafer T.
  • Chemical Communications, Vol. 48, Issue 80
  • DOI: 10.1039/c2cc35392j

Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport
journal, May 2018


Solution-Processed, Organophilic Membrane Derived from a Polymer of Intrinsic Microporosity
journal, March 2004

  • Budd, P. M.; Elabas, E. S.; Ghanem, B. S.
  • Advanced Materials, Vol. 16, Issue 5, p. 456-459
  • DOI: 10.1002/adma.200306053

Polymer ultrapermeability from the inefficient packing of 2D chains
journal, July 2017

  • Rose, Ian; Bezzu, C. Grazia; Carta, Mariolino
  • Nature Materials, Vol. 16, Issue 9
  • DOI: 10.1038/nmat4939

Highly Selective Ionic Transport through Subnanometer Pores in Polymer Films
journal, July 2016

  • Wen, Qi; Yan, Dongxiao; Liu, Feng
  • Advanced Functional Materials, Vol. 26, Issue 32
  • DOI: 10.1002/adfm.201601689

A biomimetic redox flow battery based on flavin mononucleotide
journal, October 2016

  • Orita, Akihiro; Verde, Michael G.; Sakai, Masanori
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13230

Material design and engineering of next-generation flow-battery technologies
journal, November 2016


An Efficient Polymer Molecular Sieve for Membrane Gas Separations
journal, January 2013


Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries
journal, August 2015


Evaluation of Diels–Alder poly(phenylene) anion exchange membranes in all-vanadium redox flow batteries
journal, June 2014


Highly Conductive Anion-Exchange Membranes from Microporous Tröger's Base Polymers
journal, August 2016

  • Yang, Zhengjin; Guo, Rui; Malpass-Evans, Richard
  • Angewandte Chemie International Edition, Vol. 55, Issue 38
  • DOI: 10.1002/anie.201605916

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores
journal, February 2018


A Spirobifluorene-Based Polymer of Intrinsic Microporosity with Improved Performance for Gas Separation
journal, September 2012

  • Bezzu, C. Grazia; Carta, Mariolino; Tonkins, Alexander
  • Advanced Materials, Vol. 24, Issue 44
  • DOI: 10.1002/adma.201202393

Charge- and Size-Selective Ion Sieving Through Ti 3 C 2 T x MXene Membranes
journal, September 2015

  • Ren, Chang E.; Hatzell, Kelsey B.; Alhabeb, Mohamed
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
  • DOI: 10.1021/acs.jpclett.5b01895

Rational design of polyaromatic ionomers for alkaline membrane fuel cells with >1 W cm −2 power density
journal, January 2018

  • Maurya, Sandip; Noh, Sangtaik; Matanovic, Ivana
  • Energy & Environmental Science, Vol. 11, Issue 11
  • DOI: 10.1039/C8EE02192A

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)
journal, November 2011


Precise and Ultrafast Molecular Sieving Through Graphene Oxide Membranes
journal, February 2014


Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage
journal, January 2006

  • McKeown, Neil B.; Budd, Peter M.
  • Chemical Society Reviews, Vol. 35, Issue 8, p. 675-683
  • DOI: 10.1039/b600349d

Ultra-High Proton/Vanadium Selectivity for Hydrophobic Polymer Membranes with Intrinsic Nanopores for Redox Flow Battery
journal, June 2016

  • Chae, Il Seok; Luo, Tao; Moon, Gi Hyeon
  • Advanced Energy Materials, Vol. 6, Issue 16
  • DOI: 10.1002/aenm.201600517

Sustainable Hydrogen Production
journal, August 2004


A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries
journal, June 2018


Roll-to-roll dip coating of three different PIMs for Organic Solvent Nanofiltration
journal, July 2018


Covalent organic frameworks: a materials platform for structural and functional designs
journal, September 2016


Progress and directions in low-cost redox-flow batteries for large-scale energy storage
journal, January 2017


A redox-flow battery with an alloxazine-based organic electrolyte
journal, July 2016


Impact of Hydration and Sulfonation on the Morphology and Ionic Conductivity of Sulfonated Poly(phenylene) Proton Exchange Membranes
journal, January 2019


Parallel cylindrical water nanochannels in Nafion fuel-cell membranes
journal, December 2007

  • Schmidt-Rohr, Klaus; Chen, Qiang
  • Nature Materials, Vol. 7, Issue 1
  • DOI: 10.1038/nmat2074

The synthesis, chain-packing simulation and long-term gas permeability of highly selective spirobifluorene-based polymers of intrinsic microporosity
journal, January 2018

  • Bezzu, C. Grazia; Carta, Mariolino; Ferrari, Maria-Chiara
  • Journal of Materials Chemistry A, Vol. 6, Issue 22
  • DOI: 10.1039/C8TA02601G

Full Cell Study of Diels Alder Poly(phenylene) Anion and Cation Exchange Membranes in Vanadium Redox Flow Batteries
journal, November 2015

  • Pezeshki, A. M.; Tang, Z. J.; Fujimoto, C.
  • Journal of The Electrochemical Society, Vol. 163, Issue 1
  • DOI: 10.1149/2.0201601jes

Metal–organic framework-based separator for lithium–sulfur batteries
journal, June 2016


Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability
journal, March 2017


Alkaline quinone flow battery
journal, September 2015


Advanced porous membranes with ultra-high selectivity and stability for vanadium flow batteries
journal, January 2016

  • Yuan, Zhizhang; Duan, Yinqi; Zhang, Hongzhang
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE02896E

Fundamental water and salt transport properties of polymeric materials
journal, January 2014


Porous Organic Cage Thin Films and Molecular-Sieving Membranes
journal, January 2016


Nanocrack-regulated self-humidifying membranes
journal, April 2016

  • Park, Chi Hoon; Lee, So Young; Hwang, Doo Sung
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/nature17634

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Flow Batteries: Current Status and Trends
journal, September 2015

  • Soloveichik, Grigorii L.
  • Chemical Reviews, Vol. 115, Issue 20
  • DOI: 10.1021/cr500720t

Tunable sieving of ions using graphene oxide membranes
journal, April 2017

  • Abraham, Jijo; Vasu, Kalangi S.; Williams, Christopher D.
  • Nature Nanotechnology, Vol. 12, Issue 6
  • DOI: 10.1038/nnano.2017.21

Water filtration performance of a lyotropic liquid crystal polymer membrane with uniform, sub-1-nm pores
journal, January 2011

  • Hatakeyama, Evan S.; Gabriel, Christopher J.; Wiesenauer, Brian R.
  • Journal of Membrane Science, Vol. 366, Issue 1-2
  • DOI: 10.1016/j.memsci.2010.09.028

Alkaline Quinone Flow Battery with Long Lifetime at pH 12
journal, September 2018


Alkaline Benzoquinone Aqueous Flow Battery for Large-Scale Storage of Electrical Energy
journal, December 2017

  • Yang, Zhengjin; Tong, Liuchuan; Tabor, Daniel P.
  • Advanced Energy Materials, Vol. 8, Issue 8
  • DOI: 10.1002/aenm.201702056

Molecular Modeling and Gas Permeation Properties of a Polymer of Intrinsic Microporosity Composed of Ethanoanthracene and Tröger’s Base Units
journal, November 2014

  • Tocci, Elena; De Lorenzo, Luana; Bernardo, Paola
  • Macromolecules, Vol. 47, Issue 22
  • DOI: 10.1021/ma501469m

Materials for next-generation desalination and water purification membranes
journal, April 2016

  • Werber, Jay R.; Osuji, Chinedum O.; Elimelech, Menachem
  • Nature Reviews Materials, Vol. 1, Issue 5
  • DOI: 10.1038/natrevmats.2016.18

A metal-free organic–inorganic aqueous flow battery
journal, January 2014

  • Huskinson, Brian; Marshak, Michael P.; Suh, Changwon
  • Nature, Vol. 505, Issue 7482, p. 195-198
  • DOI: 10.1038/nature12909