Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces
Abstract
Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as “dead zone” to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolytemore »
- Authors:
-
[1];
[1];
[2];
[1];
[1]
- Pohang Univ. of Science and Technology (POSTECH) (South Korea)
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE; National Research Foundation of Korea (NRF)
- OSTI Identifier:
- 1864843
- Grant/Contract Number:
- AC02-06CH11357; 2017R1A2B3004763; 2017R1A5A1015365; 2018M3D1A1058624; 2021R1C1C1009323
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 118; Journal Issue: 32; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; interfaces; low symmetry morphology; charged block copolymers; electrostatic interactions; ionic conductivity
Citation Formats
Min, Jaemin, Jung, Ha Young, Jeong, Seungwon, Lee, Byeongdu, Son, Chang Yun, and Park, Moon Jeong. Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces. United States: N. p., 2021.
Web. doi:10.1073/pnas.2107987118.
Min, Jaemin, Jung, Ha Young, Jeong, Seungwon, Lee, Byeongdu, Son, Chang Yun, & Park, Moon Jeong. Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces. United States. https://doi.org/10.1073/pnas.2107987118
Min, Jaemin, Jung, Ha Young, Jeong, Seungwon, Lee, Byeongdu, Son, Chang Yun, and Park, Moon Jeong. Tue .
"Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces". United States. https://doi.org/10.1073/pnas.2107987118. https://www.osti.gov/servlets/purl/1864843.
@article{osti_1864843,
title = {Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces},
author = {Min, Jaemin and Jung, Ha Young and Jeong, Seungwon and Lee, Byeongdu and Son, Chang Yun and Park, Moon Jeong},
abstractNote = {Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as “dead zone” to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.},
doi = {10.1073/pnas.2107987118},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 32,
volume = 118,
place = {United States},
year = {Tue Aug 03 00:00:00 EDT 2021},
month = {Tue Aug 03 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Anomalous Phase Behavior of Ionic Polymer Blends and Ionic Copolymers
journal, June 2017
- Pryamitsyn, Victor A.; Kwon, Ha-Kyung; Zwanikken, Jos W.
- Macromolecules, Vol. 50, Issue 13
Conformational Asymmetry and Quasicrystal Approximants in Linear Diblock Copolymers
journal, May 2017
- Schulze, Morgan W.; Lewis, Ronald M.; Lettow, James H.
- Physical Review Letters, Vol. 118, Issue 20
An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase
journal, January 2020
- Lachmayr, Kätchen K.; Wentz, Charlotte M.; Sita, Lawrence R.
- Angewandte Chemie International Edition, Vol. 59, Issue 4
The size and affinity effect of counterions on self-assembly of charged block copolymers
journal, March 2020
- Jiang, Jiadi; Chen, Xu; Yang, Shuang
- The Journal of Chemical Physics, Vol. 152, Issue 12
Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation
journal, November 2007
- Park, Moon Jeong; Downing, Kenneth H.; Jackson, Andrew
- Nano Letters, Vol. 7, Issue 11
Quasicrystals and Their Approximants in a Crystalline–Amorphous Diblock Copolymer
journal, March 2021
- Mueller, Andreas J.; Lindsay, Aaron P.; Jayaraman, Ashish
- Macromolecules, Vol. 54, Issue 6
Recent advances in small angle x-ray scattering for superlattice study
journal, March 2021
- Jiang, Zhang; Lee, Byeongdu
- Applied Physics Reviews, Vol. 8, Issue 1
Evaluation of the Interaction Parameter for Poly(solketal methacrylate)- block -polystyrene Copolymers
journal, January 2018
- Yu, Duk Man; Mapas, Jose Kenneth D.; Kim, Hyeyoung
- Macromolecules, Vol. 51, Issue 3
Tuning anhydrous proton conduction in single-ion polymers by crystalline ion channels
journal, November 2018
- Kim, Onnuri; Kim, Kyoungwook; Choi, U. Hyeok
- Nature Communications, Vol. 9, Issue 1
Modeling of transport of small molecules in polymer blends: Application of effective medium theory
journal, February 1983
- Sax, J.; Ottino, J. M.
- Polymer Engineering and Science, Vol. 23, Issue 3
Stable Frank–Kasper phases of self-assembled, soft matter spheres
journal, September 2018
- Reddy, Abhiram; Buckley, Michael B.; Arora, Akash
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 41
A15, σ, and a Quasicrystal: Access to Complex Particle Packings via Bidisperse Diblock Copolymer Blends
journal, January 2020
- Lindsay, Aaron P.; Lewis, Ronald M.; Lee, Bongjoon
- ACS Macro Letters, Vol. 9, Issue 2
Phase Behavior and Conductivity of Sulfonated Block Copolymers Containing Heterocyclic Diazole-Based Ionic Liquids
journal, October 2012
- Kim, Onnuri; Kim, Sung Yeon; Ahn, Hyungmin
- Macromolecules, Vol. 45, Issue 21
Emergence of a C15 Laves Phase in Diblock Polymer/Homopolymer Blends
journal, March 2020
- Mueller, Andreas J.; Lindsay, Aaron P.; Jayaraman, Ashish
- ACS Macro Letters, Vol. 9, Issue 4
Theory of Microphase Separation in Block Copolymers
journal, November 1980
- Leibler, Ludwik
- Macromolecules, Vol. 13, Issue 6
Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity
journal, January 2015
- Sing, Charles E.; Zwanikken, Jos W.; de la Cruz, Monica Olvera
- The Journal of Chemical Physics, Vol. 142, Issue 3
Phase Boundary of Frank–Kasper σ Phase in Phase Diagrams of Binary Mixtures of Block Copolymers and Homopolymers
journal, February 2019
- Takagi, Hideaki; Yamamoto, Katsuhiro
- Macromolecules, Vol. 52, Issue 5
The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity
journal, June 2002
- Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J.
- Macromolecules, Vol. 35, Issue 12
Thermodynamics and phase behavior of acid-tethered block copolymers with ionic liquids
journal, January 2017
- Jung, Ha Young; Park, Moon Jeong
- Soft Matter, Vol. 13, Issue 1
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries
journal, March 2013
- Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid
- Nature Materials, Vol. 12, Issue 5
Self-template–assisted micro-phase segregation in blended liquid-crystalline block copolymers films toward three-dimensional structures
journal, August 2020
- Hibi, Yusuke; Oguchi, Yuki; Shimizu, Yuta
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 35
Effect of Addition of a Neutral Solvent on the Order−Order and Order−Disorder Transitions in a Polystyrene- block -polyisoprene- block -polystyrene Copolymer
journal, September 1997
- Sakamoto, Naoki; Hashimoto, Takeji; Han, Chang Dae
- Macromolecules, Vol. 30, Issue 18
Self-Assembled Polymeric Supramolecular Frameworks
journal, February 2011
- Houbenov, Nikolay; Haataja, Johannes S.; Iatrou, Hermis
- Angewandte Chemie International Edition, Vol. 50, Issue 11
Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990
- Bates, Frank S.; Fredrickson, Glenn H.
- Annual Review of Physical Chemistry, Vol. 41, Issue 1
Ion Transport in Nanostructured Phosphonated Block Copolymers Containing Ionic Liquids
journal, April 2016
- Jung, Ha Young; Kim, Onnuri; Park, Moon Jeong
- Macromolecular Rapid Communications, Vol. 37, Issue 14
Manipulating the ABCs of self-assembly via low-χ block polymer design
journal, June 2017
- Chang, Alice B.; Bates, Christopher M.; Lee, Byeongdu
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 25
Effect of the Protogenic Group on the Phase Behavior and Ion Transport Properties of Acid-Bearing Block Copolymers
journal, August 2015
- Jung, Ha Young; Kim, Sung Yeon; Kim, Onnuri
- Macromolecules, Vol. 48, Issue 17
Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions
journal, October 2010
- Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong
- Nature Communications, Vol. 1, Issue 1
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers
journal, August 2014
- Xie, Nan; Li, Weihua; Qiu, Feng
- ACS Macro Letters, Vol. 3, Issue 9
Stabilizing the Frank-Kasper Phases via Binary Blends of AB Diblock Copolymers
journal, September 2016
- Liu, Meijiao; Qiang, Yicheng; Li, Weihua
- ACS Macro Letters, Vol. 5, Issue 10
Stability of the A15 phase in diblock copolymer melts
journal, June 2019
- Bates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 27
Thin Film Self-Assembly of Poly(trimethylsilylstyrene- b - d , l -lactide) with Sub-10 nm Domains
journal, October 2012
- Cushen, Julia D.; Bates, Christopher M.; Rausch, Erica L.
- Macromolecules, Vol. 45, Issue 21
Printable and Rewritable Full Block Copolymer Structural Color
journal, May 2017
- Kang, Han Sol; Lee, Jinseong; Cho, Suk Man
- Advanced Materials, Vol. 29, Issue 29
Functional Block Copolymers: Nanostructured Materials with Emerging Applications
journal, July 2012
- Schacher, Felix H.; Rupar, Paul A.; Manners, Ian
- Angewandte Chemie International Edition, Vol. 51, Issue 32
Conformational and Dynamic Properties of Poly(ethylene oxide) in BMIM + BF 4 – : A Microsecond Computer Simulation Study Using ab Initio Force Fields
journal, July 2018
- Son, Chang Yun; McDaniel, Jesse G.; Cui, Qiang
- Macromolecules, Vol. 51, Issue 14
General Synthetic Route to Cell-Permeable Block Copolymers via ROMP
journal, May 2009
- Kolonko, Erin M.; Pontrello, Jason K.; Mangold, Shane L.
- Journal of the American Chemical Society, Vol. 131, Issue 21
All‐Solid‐State Lithium–Organic Batteries Comprising Single‐Ion Polymer Nanoparticle Electrolytes
journal, April 2020
- Kim, Boram; Kang, Haneol; Kim, Kyoungwook
- ChemSusChem, Vol. 13, Issue 9
Structure and Dynamics of Concentrated Solutions of Asymmetric Block Copolymers in Slightly Selective Solvents
journal, January 1996
- Lodge, T. P.; Xu, X.; Ryu, C. Y.
- Macromolecules, Vol. 29, Issue 18
First-Principles United Atom Force Field for the Ionic Liquid BMIM + BF 4 – : An Alternative to Charge Scaling
journal, March 2016
- Son, Chang Yun; McDaniel, Jesse G.; Schmidt, J. R.
- The Journal of Physical Chemistry B, Vol. 120, Issue 14
Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer
journal, February 2019
- Jayaraman, Ashish; Zhang, Diana Y.; Dewing, Beth L.
- ACS Central Science, Vol. 5, Issue 4
Strongly Phase-Segregating Block Copolymers with Sub-20 nm Features
journal, July 2013
- Kempe, Kristian; Killops, Kato L.; Poelma, Justin E.
- ACS Macro Letters, Vol. 2, Issue 8
Electrochemical Applications of Microphase‐Separated Block Copolymer Thin Films
journal, July 2018
- Ito, Takashi; Ghimire, Govinda
- ChemElectroChem, Vol. 5, Issue 20
Building Less Tortuous Ion-Conduction Pathways Using Block Copolymer Electrolytes with a Well-Defined Cubic Symmetry
journal, December 2015
- Kim, Onnuri; Kim, Sung Yeon; Lee, Joungphil
- Chemistry of Materials, Vol. 28, Issue 1
Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008
- Park, Moon Jeong; Balsara, Nitash P.
- Macromolecules, Vol. 41, Issue 10
Frank–Kasper Phases Identified in PDMS‐ b ‐PTFEA Copolymers with High Conformational Asymmetry
journal, July 2019
- Jeon, Seungbae; Jun, Taesuk; Jo, Seongjun
- Macromolecular Rapid Communications, Vol. 40, Issue 19
Superlattice by charged block copolymer self-assembly
journal, May 2019
- Shim, Jimin; Bates, Frank S.; Lodge, Timothy P.
- Nature Communications, Vol. 10, Issue 1
Formation of a C15 Laves Phase with a Giant Unit Cell in Salt-Doped A/B/AB Ternary Polymer Blends
journal, August 2020
- Xie, Shuyi; Lindsay, Aaron P.; Bates, Frank S.
- ACS Nano, Vol. 14, Issue 10
One-volt-driven superfast polymer actuators based on single-ion conductors
journal, November 2016
- Kim, Onnuri; Kim, Hoon; Choi, U. Hyeok
- Nature Communications, Vol. 7, Issue 1
Electrostatic control of block copolymer morphology
journal, June 2014
- Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica
- Nature Materials, Vol. 13, Issue 7
Thermodynamics of Block Copolymers with and without Salt
journal, December 2013
- Teran, Alexander A.; Balsara, Nitash P.
- The Journal of Physical Chemistry B, Vol. 118, Issue 1
Interfaces in Diblocks: A Study of Miktoarm Star Copolymers
journal, September 2004
- Grason, Gregory M.; Kamien, Randall D.
- Macromolecules, Vol. 37, Issue 19