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Title: Ion Correlation Effects in Salt-Doped Block Copolymers

Abstract

Here, we apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at same coarse grained level. We show good agreement with molecular dynamics simulations.

Authors:
 [1];  [2];  [1]
+ Show Author Affiliations
  1. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
  2. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering; LG Chem, Ltd., Daejeon (Korea, Republic of). LG Chem Research Park
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1468577
Alternate Identifier(s):
OSTI ID: 1427878
Grant/Contract Number:  
SC0014458; SC0014209; 1454343
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 120; Journal Issue: 12; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; classical statistical mechanics; block copolymers; molecular dynamics

Citation Formats

Brown, Jonathan R., Seo, Youngmi, and Hall, Lisa M. Ion Correlation Effects in Salt-Doped Block Copolymers. United States: N. p., 2018. Web. doi:10.1103/PhysRevLett.120.127801.
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Brown, Jonathan R., Seo, Youngmi, & Hall, Lisa M. Ion Correlation Effects in Salt-Doped Block Copolymers. United States. https://doi.org/10.1103/PhysRevLett.120.127801
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Brown, Jonathan R., Seo, Youngmi, and Hall, Lisa M. Thu . "Ion Correlation Effects in Salt-Doped Block Copolymers". United States. https://doi.org/10.1103/PhysRevLett.120.127801. https://www.osti.gov/servlets/purl/1468577.
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@article{osti_1468577,
title = {Ion Correlation Effects in Salt-Doped Block Copolymers},
author = {Brown, Jonathan R. and Seo, Youngmi and Hall, Lisa M.},
abstractNote = {Here, we apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at same coarse grained level. We show good agreement with molecular dynamics simulations.},
doi = {10.1103/PhysRevLett.120.127801},
journal = {Physical Review Letters},
number = 12,
volume = 120,
place = {United States},
year = {Thu Mar 22 00:00:00 EDT 2018},
month = {Thu Mar 22 00:00:00 EDT 2018}
}
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Journal Article:
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https://doi.org/10.1103/PhysRevLett.120.127801
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Works referenced in this record:

Lithium environment in PEO-LiClO 4 polymer electrolyte
journal, May 2001

Multiscale Simulations of Lamellar PS–PEO Block Copolymers Doped with LiPF 6 Ions
journal, May 2017

Statistical field theory description of inhomogeneous polarizable soft matter
journal, October 2016

  • Martin, Jonathan M.; Li, Wei; Delaney, Kris T.
  • The Journal of Chemical Physics, Vol. 145, Issue 15
  • DOI: 10.1063/1.4964680

Tuning Block Polymer Structure, Properties, and Processability for the Design of Efficient Nanostructured Materials Systems
journal, January 2017

  • Morris, Melody A.; Gartner, Thomas E.; Epps, Thomas H.
  • Macromolecular Chemistry and Physics, Vol. 218, Issue 5
  • DOI: 10.1002/macp.201600513

Ion Transport Properties of Self-Assembled Polymer Electrolytes: The Role of Confinement and Interface
journal, June 2013

  • Kim, Onnuri; Jo, Gyuha; Park, Yong Jun
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 13
  • DOI: 10.1021/jz4009536

Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects
journal, April 2009

  • Young, Wen-Shiue; Epps, Thomas H.
  • Macromolecules, Vol. 42, Issue 7
  • DOI: 10.1021/ma802799p

Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling
journal, December 2014

  • Gilbert, Jonathan B.; Luo, Ming; Shelton, Cameron K.
  • ACS Nano, Vol. 9, Issue 1
  • DOI: 10.1021/nn505744r

Simple Route for Tuning the Morphology and Conductivity of Polymer Electrolytes: One End Functional Group is Enough
journal, October 2013

  • Jo, Gyuha; Ahn, Hyungmin; Park, Moon Jeong
  • ACS Macro Letters, Vol. 2, Issue 11
  • DOI: 10.1021/mz400468m

Comparison of efficient techniques for the simulation of dielectric objects in electrolytes
journal, June 2015

Crystallite dissolution in PEO-based polymers induced by water sorption
journal, September 2016

Using tapered interfaces to manipulate nanoscale morphologies in ion-doped block polymers
journal, May 2015

  • Kuan, Wei-Fan; Reed, Ellen H.; Nguyen, Ngoc A.
  • MRS Communications, Vol. 5, Issue 2
  • DOI: 10.1557/mrc.2015.19

Free-energy model for the inhomogeneous hard-sphere fluid mixture and density-functional theory of freezing
journal, August 1989

Factors Affecting Electromechanical Properties of Ionic Polymer Actuators Based on Ionic Liquid-Containing Sulfonated Block Copolymers
journal, June 2014

  • Kim, Onnuri; Kim, Sung Yeon; Park, Byungrak
  • Macromolecules, Vol. 47, Issue 13
  • DOI: 10.1021/ma500869h

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
  • DOI: 10.1063/1.4905830

Ion transport in sulfonated polymers
journal, February 2013

  • Park, Moon Jeong; Kim, Sung Yeon
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 7
  • DOI: 10.1002/polb.23257

Thermodynamics of Ion-Containing Polymer Blends and Block Copolymers
journal, November 2011

Modified interfacial statistical associating fluid theory: A perturbation density functional theory for inhomogeneous complex fluids
journal, December 2007

  • Jain, Shekhar; Dominik, Aleksandra; Chapman, Walter G.
  • The Journal of Chemical Physics, Vol. 127, Issue 24
  • DOI: 10.1063/1.2806932

Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes
journal, March 2009

  • Gomez, Enrique D.; Panday, Ashoutosh; Feng, Edward H.
  • Nano Letters, Vol. 9, Issue 3
  • DOI: 10.1021/nl900091n

A New Method for Measuring Dielectric Constant and Loss in the Range of Centimeter Waves
journal, July 1946

  • Roberts, S.; Von Hippel, A.
  • Journal of Applied Physics, Vol. 17, Issue 7
  • DOI: 10.1063/1.1707760

Thermodynamics of Salt-Doped Block Copolymers
journal, July 2014

  • Nakamura, Issei; Wang, Zhen-Gang
  • ACS Macro Letters, Vol. 3, Issue 8
  • DOI: 10.1021/mz500301z

Polymer Electrolytes
journal, July 2013

Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter
journal, January 2012

Mechanism of Ion Transport in Amorphous Poly(ethylene oxide)/LiTFSI from Molecular Dynamics Simulations
journal, February 2006

  • Borodin, Oleg; Smith, Grant D.
  • Macromolecules, Vol. 39, Issue 4
  • DOI: 10.1021/ma052277v

Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013

  • Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1
  • DOI: 10.1002/polb.23404

Diffusion of Selective Penetrants in Interfacially Modified Block Copolymers from Molecular Dynamics Simulations
journal, March 2017

Dielectric study of Polycaprolactone: A biodegradable polymer
conference, July 2016

  • Hegde, V. J.; Gallot-Lavallee, O.; Heux, L.
  • 2016 IEEE International Conference on Dielectrics (ICD)
  • DOI: 10.1109/ICD.2016.7547602

A Theoretical Study of Phase Behaviors for Diblock Copolymers in Selective Solvents
journal, September 2009

  • Suo, Tongchuan; Yan, Dadong; Yang, Shuang
  • Macromolecules, Vol. 42, Issue 17
  • DOI: 10.1021/ma900939u

Harnessing the Power of Plastics: Nanostructured Polymer Systems in Lithium-Ion Batteries
journal, August 2017

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
  • DOI: 10.1002/marc.201600036

Interfacial Behavior in Polyelectrolyte Blends: Hybrid Liquid-State Integral Equation and Self-Consistent Field Theory Study
journal, October 2013

Effects of Ion Solvation on the Miscibility of Binary Polymer Blends †
journal, December 2008

  • Wang, Zhen-Gang
  • The Journal of Physical Chemistry B, Vol. 112, Issue 50
  • DOI: 10.1021/jp806897t

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

  • Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900451e

Ordering Transition in Salt-Doped Diblock Copolymers
journal, April 2016

Relation between the Ion Size and Pore Size for an Electric Double-Layer Capacitor
journal, March 2008

  • Largeot, Celine; Portet, Cristelle; Chmiola, John
  • Journal of the American Chemical Society, Vol. 130, Issue 9
  • DOI: 10.1021/ja7106178

Polymer electrolytes integrated with ionic liquids for future electrochemical devices
journal, February 2013

  • Park, Moon Jeong; Choi, Ilyoung; Hong, Jaewan
  • Journal of Applied Polymer Science, Vol. 129, Issue 5
  • DOI: 10.1002/app.39064

Communication— 7 Li MRI Unveils Concentration Dependent Diffusion in Polymer Electrolyte Batteries
journal, January 2016

  • Chandrashekar, S.; Oparaji, Onyekachi; Yang, Guang
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0681614jes

Dynamics of entangled linear polymer melts:  A molecular‐dynamics simulation
journal, April 1990

  • Kremer, Kurt; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 92, Issue 8
  • DOI: 10.1063/1.458541

Phase Behavior of Styrene−Isoprene Diblock Copolymers in Strongly Selective Solvents
journal, January 2002

  • Lai, Chiajen; Russel, William B.; Register, Richard A.
  • Macromolecules, Vol. 35, Issue 3
  • DOI: 10.1021/ma011696z

An electrochemical approach to measuring oxidative stability of solid polymer electrolytes for lithium batteries
journal, November 2016

  • Hallinan, Daniel T.; Rausch, Alexander; McGill, Brandon
  • Chemical Engineering Science, Vol. 154
  • DOI: 10.1016/j.ces.2016.06.054

Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers
journal, February 2018

Dynamic mechanical and dielectric relaxations of polystyrene below the glass temperature
journal, April 1971

  • Yano, Okimichi; Wada, Yasaku
  • Journal of Polymer Science Part A-2: Polymer Physics, Vol. 9, Issue 4
  • DOI: 10.1002/pol.1971.160090409

Criticality and Connectivity in Macromolecular Charge Complexation
journal, November 2016

Image method for electrostatic energy of polarizable dipolar spheres
journal, August 2017

  • Gustafson, Kyle S.; Xu, Guoxi; Freed, Karl F.
  • The Journal of Chemical Physics, Vol. 147, Issue 6
  • DOI: 10.1063/1.4997620

Parallel Segregated Schur Complement Methods for Fluid Density Functional Theories
journal, January 2007

  • Heroux, Michael A.; Salinger, Andrew G.; Frink, Laura J. D.
  • SIAM Journal on Scientific Computing, Vol. 29, Issue 5
  • DOI: 10.1137/060661594

A Dielectric Study of the Effects of Melting on Molecular Relaxation in Poly(ethylene oxide) and Polyoxymethylene
journal, September 1971

Nuclear magnetic relaxation study of poly(ethylene oxide)–lithium salt based electrolytes
journal, June 1993

  • Donoso, J. P.; Bonagamba, T. J.; Panepucci, H. C.
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464435

Structure of Liquid PEO-LiTFSI Electrolyte
journal, June 2000

Salt-induced microphase separation in poly(ε-caprolactone)-b-poly(ethylene oxide) block copolymer
journal, May 2013

Fluctuation in electrolyte solutions: The self energy
journal, February 2010

Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts
journal, October 2010

  • Wanakule, Nisita S.; Virgili, Justin M.; Teran, Alexander A.
  • Macromolecules, Vol. 43, Issue 19
  • DOI: 10.1021/ma1013786

Coarse-Grained Model of the Dynamics of Electrolyte Solutions
journal, August 2017

  • Andreev, Marat; Chremos, Alexandros; de Pablo, Juan
  • The Journal of Physical Chemistry B, Vol. 121, Issue 34
  • DOI: 10.1021/acs.jpcb.7b04297

Phase Behavior of a Block Copolymer/Salt Mixture through the Order-to-Disorder Transition
journal, April 2014

  • Thelen, Jacob L.; Teran, Alexander A.; Wang, Xin
  • Macromolecules, Vol. 47, Issue 8
  • DOI: 10.1021/ma500292n

Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes
journal, October 2015

Lithium Metal Stability in Batteries with Block Copolymer Electrolytes
journal, January 2013

  • Hallinan, Daniel T.; Mullin, Scott A.; Stone, Gregory M.
  • Journal of The Electrochemical Society, Vol. 160, Issue 3
  • DOI: 10.1149/2.030303jes

A practical integral equation for the structure and thermodynamics of hard sphere Coulomb fluids
journal, August 2011

  • Zwanikken, Jos W.; Jha, Prateek K.; de la Cruz, Monica Olvera
  • The Journal of Chemical Physics, Vol. 135, Issue 6
  • DOI: 10.1063/1.3624809

Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode
journal, January 2016

  • Harry, Katherine J.; Higa, Kenneth; Srinivasan, Venkat
  • Journal of The Electrochemical Society, Vol. 163, Issue 10
  • DOI: 10.1149/2.0191610jes

Miscible blend dynamics and the length scale of local compositions
journal, January 2005

  • García Sakai, Victoria; Maranas, Janna K.; Chowdhuri, Zema
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 20
  • DOI: 10.1002/polb.20562

Towards a microscopic theory of wetting by ionic solutions. I. Surface properties of the semi-primitive model
journal, September 2006

A Study of the dielectric properties of the polymer electrolyte PEO-LiClO4 over a composition range using time domain spectroscopy
journal, September 1989

  • Gray, F. M.; Vincent, C. A.; Kent, M.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 27, Issue 10
  • DOI: 10.1002/polb.1989.090271006

Designing Polymer Electrolytes for Safe and High Capacity Rechargeable Lithium Batteries
journal, March 2017

First-Order Disordered-to-Lamellar Phase Transition in Lithium Salt-Doped Block Copolymers
journal, May 2013

  • Nakamura, Issei; Balsara, Nitash P.; Wang, Zhen-Gang
  • ACS Macro Letters, Vol. 2, Issue 6
  • DOI: 10.1021/mz4001404

Correlations and free energies in restricted primitive model descriptions of electrolytes
journal, January 1993

  • Hummer, Gerhard; Soumpasis, Dikeos Mario
  • The Journal of Chemical Physics, Vol. 98, Issue 1
  • DOI: 10.1063/1.464600

Controlled ionic conductivity via tapered block polymer electrolytes
journal, January 2015

  • Kuan, Wei-Fan; Remy, Roddel; Mackay, Michael E.
  • RSC Advances, Vol. 5, Issue 17
  • DOI: 10.1039/C4RA15953E

Enhanced Performance in Lithium–Polymer Batteries Using Surface-Functionalized Si Nanoparticle Anodes and Self-Assembled Block Copolymer Electrolytes
journal, September 2011

  • Choi, Ilyoung; Ahn, Hyungmin; Park, Moon Jeong
  • Macromolecules, Vol. 44, Issue 18
  • DOI: 10.1021/ma200796k

Fast low-voltage electroactive actuators using nanostructured polymer electrolytes
journal, July 2013

  • Kim, Onnuri; Shin, Tae Joo; Park, Moon Jeong
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3208

Efficient continuum model for simulating polymer blends and copolymers
journal, December 1996

  • Grest, Gary S.; Lacasse, Martin‐D.; Kremer, Kurt
  • The Journal of Chemical Physics, Vol. 105, Issue 23
  • DOI: 10.1063/1.472978

Fundamental measure theory for hard-sphere mixtures: a review
journal, January 2010

Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit
journal, February 2016

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
  • DOI: 10.1038/nmat4001

Ionic Conductivity of Block Copolymer Electrolytes in the Vicinity of Order−Disorder and Order−Order Transitions
journal, August 2009

  • Wanakule, Nisita S.; Panday, Ashoutosh; Mullin, Scott A.
  • Macromolecules, Vol. 42, Issue 15
  • DOI: 10.1021/ma900401a

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
  • DOI: 10.1021/jp408079z

Fluids density functional theory and initializing molecular dynamics simulations of block copolymers
journal, March 2016

  • Brown, Jonathan R.; Seo, Youngmi; Maula, Tiara Ann D.
  • The Journal of Chemical Physics, Vol. 144, Issue 12
  • DOI: 10.1063/1.4943982

Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation
journal, April 2006

  • Cochran, Eric W.; Garcia-Cervera, Carlos J.; Fredrickson, Glenn H.
  • Macromolecules, Vol. 39, Issue 7
  • DOI: 10.1021/ma0527707

Stable and unstable phases of a diblock copolymer melt
journal, April 1994

Dielectric Effects in the Self-Assembly of Binary Colloidal Aggregates
journal, July 2014

Dielectric effects in the self-assembly of binary colloidal aggregates
text, January 2014

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