Ionic conductivity and counterion condensation in nanoconfined polycation and polyanion brushes prepared from block copolymer templates

Arges, Christopher G.; Li, Ke; Zhang, Le; Kambe, Yu; Wu, Guang-Peng; Lwoya, Baraka; Albert, Julie N.  L.; Nealey, Paul F.; Kumar, Revati

doi:10.1039/c8me00081f

Ionic conductivity and counterion condensation in nanoconfined polycation and polyanion brushes prepared from block copolymer templates

Journal Article · Fri Feb 08 00:00:00 EST 2019 · Molecular Systems Design & Engineering

DOI:https://doi.org/10.1039/c8me00081f· OSTI ID:1558007

^[1]; Li, Ke ^[1]; ^[1]; ^[2]; ^[3]; Lwoya, Baraka ^[4]; ^[4]; ^[2]; ^[1]

Louisiana State Univ., Baton Rouge, LA (United States)
Univ. of Chicago, IL (United States)
Zhejiang Univ., Hangzhou (China).
Tulane Univ., New Orleans, LA (United States)

Microphase separated block copolymer electrolyte (BCE) systems are attractive candidates for electrochemical systems because the concentrated ionic groups in one block provide pathways for facile ion transport while the non-ionic block bestows mechanical integrity and suppresses excess water uptake. Numerous researchers have prepared and studied bulk BCEs as ion conductors, but these materials inherent complex nature and imprecise architecture makes it difficult to extract definitive conclusions how the macromolecular structure influences ion transport. In this work, the process of block copolymer lithography was demonstrated to create model nano-confined polymer electrolyte brushes that mimic lamellae structures found in bulk BCE membranes. Both nano-confined anion and cation conducting polymer brushes were prepared and excellent ionic conductivities (10^-2 S cm^-1 to 10^-1 S cm^-1) were obtained.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; SC0018989

OSTI ID:: 1558007

Alternate ID(s):: OSTI ID: 1495827

Journal Information:: Molecular Systems Design & Engineering, Journal Name: Molecular Systems Design & Engineering Journal Issue: 2 Vol. 4; ISSN 2058-9689; ISSN MSDEBG

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Impact of Substrate and Processing on Confinement of Nafion Thin Films Kusoglu, Ahmet; Kushner, Douglas; Paul, Devproshad K. Advanced Functional Materials, Vol. 24, Issue 30 https://doi.org/10.1002/adfm.201304311	journal	April 2014
Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application Cummins, Cian; Ghoshal, Tandra; Holmes, Justin D. Advanced Materials, Vol. 28, Issue 27 https://doi.org/10.1002/adma.201503432	journal	January 2016
Epoxide-substituted vinyl and acrylate copolymers Simms, J. A. Journal of Applied Polymer Science, Vol. 5, Issue 13 https://doi.org/10.1002/app.1961.070051309	journal	January 1961
Bridging contributions to polyelectrolyte brush collapse in multivalent salt solutions Brettmann, Blair Kathryn; Laugel, Nicolas; Hoffmann, Norman Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 2 https://doi.org/10.1002/pola.27959	journal	November 2015
Block copolymer electrolytes for rechargeable lithium batteries Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H. Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1 https://doi.org/10.1002/polb.23404	journal	November 2013
Electrochemical sensors with solid polymer electrolytes Opekar, František; Štulı́k, Karel Analytica Chimica Acta, Vol. 385, Issue 1-3 https://doi.org/10.1016/S0003-2670(98)00583-2	journal	April 1999
Block copolymers and conventional lithography Stoykovich, Mark P.; Nealey, Paul F. Materials Today, Vol. 9, Issue 9, p. 20-29 https://doi.org/10.1016/S1369-7021(06)71619-4	journal	September 2006
Triblock copolymer ionomer membranes Elabd, Yossef A.; Walker, Charles W.; Beyer, Frederick L. Journal of Membrane Science, Vol. 231, Issue 1-2 https://doi.org/10.1016/j.memsci.2003.11.019	journal	March 2004
Accounting for frame of reference and thermodynamic non-idealities when calculating salt diffusion coefficients in ion exchange membranes Kamcev, Jovan; Paul, Donald R.; Manning, Gerald S. Journal of Membrane Science, Vol. 537 https://doi.org/10.1016/j.memsci.2017.05.034	journal	September 2017
Effect of fixed charge group concentration on salt permeability and diffusion coefficients in ion exchange membranes Kamcev, Jovan; Doherty, Cara M.; Lopez, Kian P. Journal of Membrane Science, Vol. 566 https://doi.org/10.1016/j.memsci.2018.08.053	journal	November 2018
Directed self-assembly of block copolymers on chemical patterns: A platform for nanofabrication Ji, Shengxiang; Wan, Lei; Liu, Chi-Chun Progress in Polymer Science, Vol. 54-55 https://doi.org/10.1016/j.progpolymsci.2015.10.006	journal	March 2016
Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon Chemistry of Materials, Vol. 28, Issue 5 https://doi.org/10.1021/acs.chemmater.5b04452	journal	January 2016
Effect of Lithium-Ion Concentration on Morphology and Ion Transport in Single-Ion-Conducting Block Copolymer Electrolytes Rojas, Adriana A.; Inceoglu, Sebnem; Mackay, Nikolaus G. Macromolecules, Vol. 48, Issue 18 https://doi.org/10.1021/acs.macromol.5b01193	journal	September 2015
Ion Activity Coefficients in Ion Exchange Polymers: Applicability of Manning’s Counterion Condensation Theory Kamcev, Jovan; Paul, Donald R.; Freeman, Benny D. Macromolecules, Vol. 48, Issue 21 https://doi.org/10.1021/acs.macromol.5b01654	journal	October 2015
Ion Diffusion Coefficients in Ion Exchange Membranes: Significance of Counterion Condensation Kamcev, Jovan; Paul, Donald R.; Manning, Gerald S. Macromolecules, Vol. 51, Issue 15 https://doi.org/10.1021/acs.macromol.8b00645	journal	July 2018
Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes Kamcev, Jovan; Paul, Donald R.; Manning, Gerald S. ACS Applied Materials & Interfaces, Vol. 9, Issue 4 https://doi.org/10.1021/acsami.6b14902	journal	January 2017
Harvesting Waste Heat in Unipolar Ion Conducting Polymers Chang, William B.; Evans, Christopher M.; Popere, Bhooshan C. ACS Macro Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsmacrolett.5b00829	journal	December 2015
Electrochemical Effects in Thermoelectric Polymers Chang, William B.; Fang, Haiyu; Liu, Jun ACS Macro Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsmacrolett.6b00054	journal	March 2016
Comparing Solvophobic and Multivalent Induced Collapse in Polyelectrolyte Brushes Jackson, Nicholas E.; Brettmann, Blair K.; Vishwanath, Venkatram ACS Macro Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsmacrolett.6b00837	journal	January 2017
Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement Diederichsen, Kyle M.; Brow, Ryan R.; Stoykovich, Mark P. ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/acsnano.5b01321	journal	February 2015
Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b04202	journal	September 2018
Ion-Exchange Membranes in the Chemical Process Industry Strathmann, Heiner; Grabowski, Andrej; Eigenberger, Gerhart Industrial & Engineering Chemistry Research, Vol. 52, Issue 31 https://doi.org/10.1021/ie4002102	journal	April 2013
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment Majewski, Pawel W.; Gopinadhan, Manesh; Jang, Woo-Sik Journal of the American Chemical Society, Vol. 132, Issue 49 https://doi.org/10.1021/ja107309p	journal	December 2010
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
An Improved Multistate Empirical Valence Bond Model for Aqueous Proton Solvation and Transport ^† Wu, Yujie; Chen, Hanning; Wang, Feng The Journal of Physical Chemistry B, Vol. 112, Issue 2 https://doi.org/10.1021/jp076658h	journal	January 2008
An Improved Multistate Empirical Valence Bond Model for Aqueous Proton Solvation and Transport Wu, Yujie; Chen, Hanning; Wang, Feng The Journal of Physical Chemistry B, Vol. 112, Issue 23 https://doi.org/10.1021/jp8036318	journal	June 2008
A Study of Polyelectrolyte Brushes Formed from Adsorption of Amphiphilic Diblock Copolymers Using the Surface Forces Apparatus Balastre, Marc; Li, Feng; Schorr, Phillip Macromolecules, Vol. 35, Issue 25 https://doi.org/10.1021/ma011875g	journal	December 2002
Block Copolymers for Fuel Cells Elabd, Yossef A.; Hickner, Michael A. Macromolecules, Vol. 44, Issue 1 https://doi.org/10.1021/ma101247c	journal	January 2011
Ionic Conductivity of Nanostructured Block Copolymer/Ionic Liquid Membranes Hoarfrost, Megan L.; Segalman, Rachel A. Macromolecules, Vol. 44, Issue 13 https://doi.org/10.1021/ma200060g	journal	July 2011
Counterion Condensation in Nafion Beers, Keith M.; Hallinan, Daniel T.; Wang, Xin Macromolecules, Vol. 44, Issue 22 https://doi.org/10.1021/ma2015084	journal	November 2011
Self-Assembly and Transport Limitations in Confined Nafion Films Modestino, Miguel A.; Paul, Devproshad K.; Dishari, Shudipto Macromolecules, Vol. 46, Issue 3, p. 867-873 https://doi.org/10.1021/ma301999a	journal	January 2013
Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers Li, Nanwen; Guiver, Michael D. Macromolecules, Vol. 47, Issue 7 https://doi.org/10.1021/ma402254h	journal	February 2014
Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte Chintapalli, Mahati; Chen, X. Chelsea; Thelen, Jacob L. Macromolecules, Vol. 47, Issue 15 https://doi.org/10.1021/ma501202c	journal	July 2014
Nanoparticle-Driven Assembly of Highly Conducting Hybrid Block Copolymer Electrolytes Villaluenga, Irune; Chen, Xi Chelsea; Devaux, Didier Macromolecules, Vol. 48, Issue 2 https://doi.org/10.1021/ma502234y	journal	January 2015
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Phase Behavior of Symmetric Sulfonated Block Copolymers Park, Moon Jeong; Balsara, Nitash P. Macromolecules, Vol. 41, Issue 10 https://doi.org/10.1021/ma702733f	journal	May 2008
Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains Han, Eungnak; Stuen, Karl O.; La, Young-Hye Macromolecules, Vol. 41, Issue 23 https://doi.org/10.1021/ma8018393	journal	December 2008
Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air Park, Moon Jeong; Balsara, Nitash P. Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma901980b	journal	January 2010
Direct Force Measurements at Polymer Brush Surfaces by Atomic Force Microscopy Kelley, Tommie W.; Schorr, Phillip A.; Johnson, Kristin D. Macromolecules, Vol. 31, Issue 13, p. 4297-4300 https://doi.org/10.1021/ma971571n	journal	June 1998
Screening Effects in a Polyelectrolyte Brush: Self-Consistent-Field Theory Zhulina, E. B.; Klein Wolterink, J.; Borisov, O. V. Macromolecules, Vol. 33, Issue 13 https://doi.org/10.1021/ma990187i	journal	June 2000
Conductivity Scaling Relationships for Nanostructured Block Copolymer/Ionic Liquid Membranes Hoarfrost, Megan L.; Segalman, Rachel A. ACS Macro Letters, Vol. 1, Issue 8 https://doi.org/10.1021/mz300241g	journal	July 2012
Design of Cluster-free Polymer Electrolyte Membranes and Implications on Proton Conductivity Beers, Keith M.; Balsara, Nitash P. ACS Macro Letters, Vol. 1, Issue 10 https://doi.org/10.1021/mz300389f	journal	September 2012
Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries Inceoglu, Sebnem; Rojas, Adriana A.; Devaux, Didier ACS Macro Letters, Vol. 3, Issue 6 https://doi.org/10.1021/mz5001948	journal	May 2014
Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation Park, Moon Jeong; Downing, Kenneth H.; Jackson, Andrew Nano Letters, Vol. 7, Issue 11 https://doi.org/10.1021/nl072617l	journal	November 2007
Effect of Morphology of Nanoscale Hydrated Channels on Proton Conductivity in Block Copolymer Electrolyte Membranes Chen, X. Chelsea; Wong, David T.; Yakovlev, Sergey Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl501537p	journal	June 2014
Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly Feng, Xunda; Tousley, Marissa E.; Cowan, Matthew G. ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505037b	journal	November 2014
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries Stoykovich, Mark P.; Kang, Huiman; Daoulas, Kostas Ch. ACS Nano, Vol. 1, Issue 3 https://doi.org/10.1021/nn700164p	journal	October 2007
Single-layer ionic conduction on carboxyl-terminated silane monolayers patterned by constructive lithography Berson, Jonathan; Burshtain, Doron; Zeira, Assaf Nature Materials, Vol. 14, Issue 6 https://doi.org/10.1038/nmat4254	journal	April 2015
New molecular-scale information on polystyrene dynamics in PS and PS–BaTiO ₃ composites from FTIR spectroscopy Olmos, D.; Martín, E. V.; González-Benito, J. Phys. Chem. Chem. Phys., Vol. 16, Issue 44 https://doi.org/10.1039/C4CP03516J	journal	January 2014
Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation Kamcev, Jovan; Galizia, Michele; Benedetti, Francesco M. Physical Chemistry Chemical Physics, Vol. 18, Issue 8 https://doi.org/10.1039/C5CP06747B	journal	January 2016
Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe Journal of Materials Chemistry A, Vol. 5, Issue 11 https://doi.org/10.1039/C6TA10838E	journal	January 2017
Asymmetric Faradaic systems for selective electrochemical separations Su, Xiao; Tan, Kai-Jher; Elbert, Johannes Energy & Environmental Science, Vol. 10, Issue 5 https://doi.org/10.1039/C7EE00066A	journal	January 2017
Post-polymerization modification reactions of poly(glycidyl methacrylate)s Muzammil, Ezzah M.; Khan, Anzar; Stuparu, Mihaiela C. RSC Advances, Vol. 7, Issue 88 https://doi.org/10.1039/C7RA11093F	journal	January 2017
Assessing the influence of different cation chemistries on ionic conductivity and alkaline stability of anion exchange membranes Arges, Christopher G.; Parrondo, Javier; Johnson, Graham Journal of Materials Chemistry, Vol. 22, Issue 9 https://doi.org/10.1039/c2jm14898f	journal	January 2012
Understanding anisotropic transport in self-assembled membranes and maximizing ionic conductivity by microstructure alignment Majewski, Pawel W.; Gopinadhan, Manesh; Osuji, Chinedum O. Soft Matter, Vol. 9, Issue 29 https://doi.org/10.1039/c3sm50320h	journal	January 2013
Limiting Laws and Counterion Condensation in Polyelectrolyte Solutions I. Colligative Properties Manning, Gerald S. The Journal of Chemical Physics, Vol. 51, Issue 3 https://doi.org/10.1063/1.1672157	journal	August 1969
Precipitation of highly charged polyelectrolyte solutions in the presence of multivalent salts de la Cruz, M. Olvera; Belloni, L.; Delsanti, M. The Journal of Chemical Physics, Vol. 103, Issue 13 https://doi.org/10.1063/1.470459	journal	October 1995
Molecular pathways for defect annihilation in directed self-assembly Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo Proceedings of the National Academy of Sciences, Vol. 112, Issue 46 https://doi.org/10.1073/pnas.1508225112	journal	October 2015
Charged Polymer Brushes: Counterion Incorporation and Scaling Relations Ahrens, Heiko; Förster, Stephan; Helm, Christiane A. Physical Review Letters, Vol. 81, Issue 19 https://doi.org/10.1103/PhysRevLett.81.4172	journal	November 1998
Collapse of Spherical Polyelectrolyte Brushes in the Presence of Multivalent Counterions Mei, Yu; Lauterbach, Karlheinz; Hoffmann, Martin Physical Review Letters, Vol. 97, Issue 15 https://doi.org/10.1103/PhysRevLett.97.158301	journal	October 2006
Kinetics of Oxygen Reduction on Pt(hkl) Electrodes: Implications for the Crystallite Size Effect with Supported Pt Electrocatalysts Markovic, Nenad Journal of The Electrochemical Society, Vol. 144, Issue 5 https://doi.org/10.1149/1.1837646	journal	January 1997
Proton Transport Property in Supported Nafion Nanothin Films by Electrochemical Impedance Spectroscopy Paul, Devproshad K.; McCreery, Richard; Karan, Kunal Journal of The Electrochemical Society, Vol. 161, Issue 14 https://doi.org/10.1149/2.0571414jes	journal	January 2014
Ion Conduction in Microphase-Separated Block Copolymer Electrolytes Kambe, Yu; Arges, Christopher G.; Patel, Shrayesh The Electrochemical Society Interface, Vol. 26, Issue 1 https://doi.org/10.1149/2.F07171if	journal	January 2017
Synthesis in pilot plant scale and physical properties of sulfonated polystyrene Martins, Cristiane R.; Ruggeri, Giacommo; De Paoli, Marco-A. Journal of the Brazilian Chemical Society, Vol. 14, Issue 5 https://doi.org/10.1590/S0103-50532003000500015	journal	January 2003

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Ionic conductivity and counterion condensation in nanoconfined polycation and polyanion brushes prepared from block copolymer templates

Citation Formats

References (64)

Similar Records

Related Subjects