Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

Zhang, Bo; Zheng, Caini; Sims, Michael B.; Bates, Frank S.; Lodge, Timothy P.

doi:10.1021/acsmacrolett.1c00393

Title: Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

Abstract

A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order–disorder transition temperature (T_ODT) significantly. Additionally, the effective Flory–Huggins interaction parameter (χ_eff) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. Lastly, we therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.

Authors:

^[1]; Zheng, Caini ^[1];

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States)

Publication Date:: Fri Jul 23 00:00:00 EDT 2021

Research Org.:: Univ. of Minnesota, Twin Cities, MN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1831774

Grant/Contract Number:: SC0017809

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 10; Journal Issue: 8; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; Anions; Counterions; Solvation; Copolymers; Polymers

Citation Formats


                    Zhang, Bo, Zheng, Caini, Sims, Michael B., Bates, Frank S., and Lodge, Timothy P. Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers.  United States: N. p., 2021. 
Web.  doi:10.1021/acsmacrolett.1c00393.

Copy to clipboard


                    Zhang, Bo, Zheng, Caini, Sims, Michael B., Bates, Frank S., & Lodge, Timothy P. Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers.  United States.  https://doi.org/10.1021/acsmacrolett.1c00393

Copy to clipboard


                    Zhang, Bo, Zheng, Caini, Sims, Michael B., Bates, Frank S., and Lodge, Timothy P. Fri .  
"Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers".  United States.  https://doi.org/10.1021/acsmacrolett.1c00393.  https://www.osti.gov/servlets/purl/1831774.

Copy to clipboard


                    
@article{osti_1831774,

  title        = {Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers},

  author       = {Zhang, Bo and Zheng, Caini and Sims, Michael B. and Bates, Frank S. and Lodge, Timothy P.},

  abstractNote = {A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order–disorder transition temperature (TODT) significantly. Additionally, the effective Flory–Huggins interaction parameter (χeff) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. Lastly, we therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.},

  doi          = {10.1021/acsmacrolett.1c00393},

  journal      = {ACS Macro Letters},

  number       = 8,

  volume       = 10,

  place        = {United States},

  year         = {Fri Jul 23 00:00:00 EDT 2021},

  month        = {Fri Jul 23 00:00:00 EDT 2021}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acsmacrolett.1c00393

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Effect of Lithium-Ion Concentration on Morphology and Ion Transport in Single-Ion-Conducting Block Copolymer Electrolytes
journal, September 2015

Rojas, Adriana A.; Inceoglu, Sebnem; Mackay, Nikolaus G.
Macromolecules, Vol. 48, Issue 18
DOI: 10.1021/acs.macromol.5b01193

Microphase separation of charged diblock copolymers: melts and solutions
journal, September 1992

Marko, J. F.; Rabin, Y.
Macromolecules, Vol. 25, Issue 5
DOI: 10.1021/ma00031a022

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
DOI: 10.1021/acs.macromol.7b00523

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

Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

Fredrickson, Glenn H.; Helfand, Eugene
The Journal of Chemical Physics, Vol. 87, Issue 1
DOI: 10.1063/1.453566

Synthesis and Surface Characterization of Well-Defined Amphiphilic Block Copolymers Containing Poly[oligo(ethylene glycol) methacrylate] Segments
journal, January 2006

Ishizone, Takashi; Han, Seok; Hagiwara, Mamoru
Macromolecules, Vol. 39, Issue 3
DOI: 10.1021/ma0521699

Ion-Complexation-Induced Changes in the Interaction Parameter and the Chain Conformation of PS- b -PMMA Copolymers
journal, July 2008

Wang, Jia-Yu; Chen, Wei; Russell, Thomas P.
Macromolecules, Vol. 41, Issue 13
DOI: 10.1021/ma800718z

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

Tarascon, J.-M.; Armand, M.
Nature, Vol. 414, Issue 6861, p. 359-367
DOI: 10.1038/35104644

Ionic Conduction and Dielectric Response of Poly(imidazolium acrylate) Ionomers
journal, April 2012

Choi, U. Hyeok; Lee, Minjae; Wang, Sharon
Macromolecules, Vol. 45, Issue 9
DOI: 10.1021/ma202784e

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015

Fan, Fei; Wang, Yangyang; Hong, Tao
Macromolecules, Vol. 48, Issue 13
DOI: 10.1021/acs.macromol.5b00257

Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts
journal, April 2012

Scalfani, Vincent F.; Wiesenauer, Erin F.; Ekblad, John R.
Macromolecules, Vol. 45, Issue 10
DOI: 10.1021/ma300328u

Theory of Microphase Separation in Block Copolymers
journal, November 1980

Leibler, Ludwik
Macromolecules, Vol. 13, Issue 6
DOI: 10.1021/ma60078a047

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

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

Nakamura, Issei; Balsara, Nitash P.; Wang, Zhen-Gang
Physical Review Letters, Vol. 107, Issue 19
DOI: 10.1103/PhysRevLett.107.198301

Role of Tethered Ion Placement on Polymerized Ionic Liquid Structure and Conductivity: Pendant versus Backbone Charge Placement
journal, July 2016

Evans, Christopher M.; Bridges, Colin R.; Sanoja, Gabriel E.
ACS Macro Letters, Vol. 5, Issue 8
DOI: 10.1021/acsmacrolett.6b00534

Influence of Bound Ion on the Morphology and Conductivity of Anion-Conducting Block Copolymers
journal, February 2013

Sudre, Guillaume; Inceoglu, Sebnem; Cotanda, Pepa
Macromolecules, Vol. 46, Issue 4
DOI: 10.1021/ma302357k

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

Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries
journal, January 2001

Ruzette, Anne-Valérie G.; Soo, Philip P.; Sadoway, Donald R.
Journal of The Electrochemical Society, Vol. 148, Issue 6
DOI: 10.1149/1.1368097

Polymer Electrolytes
journal, July 2013

Hallinan, Daniel T.; Balsara, Nitash P.
Annual Review of Materials Research, Vol. 43, Issue 1
DOI: 10.1146/annurev-matsci-071312-121705

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

Nakamura, Issei; Wang, Zhen-Gang
Soft Matter, Vol. 8, Issue 36
DOI: 10.1039/c2sm25606a

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990

Bates, Frank S.; Fredrickson, Glenn H.
Annual Review of Physical Chemistry, Vol. 41, Issue 1
DOI: 10.1146/annurev.pc.41.100190.002521

Self-assembly in block polyelectrolytes
journal, February 2011

Yang, Shuang; Vishnyakov, Aleksey; Neimark, Alexander V.
The Journal of Chemical Physics, Vol. 134, Issue 5
DOI: 10.1063/1.3532831

Prediction of polymer densities
journal, May 1969

Van Krevelen, D. W.; Hoftyzer, P. J.
Journal of Applied Polymer Science, Vol. 13, Issue 5
DOI: 10.1002/app.1969.070130506

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives
journal, January 2017

Zhang, Heng; Li, Chunmei; Piszcz, Michal
Chemical Society Reviews, Vol. 46, Issue 3
DOI: 10.1039/C6CS00491A

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 Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers
journal, July 2011

Weber, Ryan L.; Ye, Yuesheng; Schmitt, Andrew L.
Macromolecules, Vol. 44, Issue 14
DOI: 10.1021/ma201067h

Block Copolymers—Designer Soft Materials
journal, February 1999

Bates, Frank S.; Fredrickson, Glenn H.
Physics Today, Vol. 52, Issue 2
DOI: 10.1063/1.882522

Theory of Solutions of High Polymers ¹
journal, July 1942

Huggins, Maurice L.
Journal of the American Chemical Society, Vol. 64, Issue 7
DOI: 10.1021/ja01259a068

Anhydrous Proton Transport in Polymerized Ionic Liquid Block Copolymers: Roles of Block Length, Ionic Content, and Confinement
journal, December 2015

Evans, Christopher M.; Sanoja, Gabriel E.; Popere, Bhooshan C.
Macromolecules, Vol. 49, Issue 1
DOI: 10.1021/acs.macromol.5b02202

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt
journal, August 2018

Loo, Whitney S.; Galluzzo, Michael D.; Li, Xiuhong
The Journal of Physical Chemistry B, Vol. 122, Issue 33
DOI: 10.1021/acs.jpcb.8b04189

Network Structure and Strong Microphase Separation for High Ion Conductivity in Polymerized Ionic Liquid Block Copolymers
journal, June 2013

Choi, Jae-Hong; Ye, Yuesheng; Elabd, Yossef A.
Macromolecules, Vol. 46, Issue 13
DOI: 10.1021/ma400562a

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

Gartner, Thomas E.; Morris, Melody A.; Shelton, Cameron K.
Macromolecules, Vol. 51, Issue 5
DOI: 10.1021/acs.macromol.7b02600

Molecular Mobility and Cation Conduction in Polyether–Ester–Sulfonate Copolymer Ionomers
journal, April 2012

Tudryn, Gregory J.; O’Reilly, Michael V.; Dou, Shichen
Macromolecules, Vol. 45, Issue 9
DOI: 10.1021/ma202273j

Thermodynamics of High Polymer Solutions
journal, January 1942

Flory, Paul J.
The Journal of Chemical Physics, Vol. 10, Issue 1
DOI: 10.1063/1.1723621

Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study
journal, December 2011

Gunkel, Ilja; Thurn-Albrecht, Thomas
Macromolecules, Vol. 45, Issue 1
DOI: 10.1021/ma201334h

Microphase separation in polyelectrolytic diblock copolymer melt: Weak segregation limit
journal, June 2007

Kumar, Rajeev; Muthukumar, M.
The Journal of Chemical Physics, Vol. 126, Issue 21
DOI: 10.1063/1.2737049

Single‐Ion Conducting Polymer Electrolytes for Solid‐State Lithium–Metal Batteries: Design, Performance, and Challenges
journal, February 2021

Zhu, Jiadeng; Zhang, Zhen; Zhao, Sheng
Advanced Energy Materials, Vol. 11, Issue 14
DOI: 10.1002/aenm.202003836

Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries
journal, May 2014

Inceoglu, Sebnem; Rojas, Adriana A.; Devaux, Didier
ACS Macro Letters, Vol. 3, Issue 6
DOI: 10.1021/mz5001948

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations
journal, June 2016

Zhang, Wenxu; Liu, Ye; Jackson, Aaron C.
Macromolecules, Vol. 49, Issue 13
DOI: 10.1021/acs.macromol.6b00653

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

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

Impact of Electrostatic Interactions on the Self-Assembly of Charge-Neutral Block Copolyelectrolytes
journal, January 2020

Russell, Sebastian T.; Raghunathan, Ramya; Jimenez, Andrew M.
Macromolecules, Vol. 53, Issue 2
DOI: 10.1021/acs.macromol.9b01293

Polyelectrolyte Blends and Nontrivial Behavior in Effective Flory–Huggins Parameters
journal, July 2014

Sing, Charles E.; Olvera de la Cruz, Monica
ACS Macro Letters, Vol. 3, Issue 8
DOI: 10.1021/mz500202n

Phase Behavior and Block Sequence Effects in Lithium Perchlorate-Doped Poly(isoprene- b -styrene- b -ethylene oxide) and Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymers
journal, April 2003

Epps, Thomas H.; Bailey, Travis S.; Waletzko, Ryan
Macromolecules, Vol. 36, Issue 8
DOI: 10.1021/ma021231o

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers
journal, February 2019

Loo, Whitney S.; Balsara, Nitash P.
Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 18
DOI: 10.1002/polb.24800

Physical Properties of Polymers Handbook
book, January 2007

Mark, James E.
DOI: 10.1007/978-0-387-69002-5

Self-Assembly of Charge-Containing Copolymers at the Liquid–Liquid Interface
journal, March 2019

Jiménez-Ángeles, Felipe; Kwon, Ha-Kyung; Sadman, Kazi
ACS Central Science, Vol. 5, Issue 4
DOI: 10.1021/acscentsci.9b00084

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

Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008

Park, Moon Jeong; Balsara, Nitash P.
Macromolecules, Vol. 41, Issue 10
DOI: 10.1021/ma702733f

Superlattice by charged block copolymer self-assembly
journal, May 2019

Shim, Jimin; Bates, Frank S.; Lodge, Timothy P.
Nature Communications, Vol. 10, Issue 1
DOI: 10.1038/s41467-019-10141-z

Segmental Dynamics of Ethylene Oxide-Containing Polymers with Diverse Backbone Chemistries
journal, February 2016

Bartels, Joshua; Wang, Jing-Han Helen; Chen, Quan
Macromolecules, Vol. 49, Issue 5
DOI: 10.1021/acs.macromol.5b02423

Phase Behavior and Ionic Conductivity of Lithium Perchlorate-Doped Polystyrene- b -poly(2-vinylpyridine) Copolymer
journal, August 2011

Naidu, Sudhakar; Ahn, Hyungju; Gong, Jinsam
Macromolecules, Vol. 44, Issue 15
DOI: 10.1021/ma200429v

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation
journal, May 2020

Hou, Kevin J.; Loo, Whitney S.; Balsara, Nitash P.
Macromolecules, Vol. 53, Issue 10
DOI: 10.1021/acs.macromol.0c00559

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

Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017

Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
Nature Reviews Materials, Vol. 2, Issue 4
DOI: 10.1038/natrevmats.2016.103

Solvation and Entropic Regimes in Ion-Containing Block Copolymers
journal, September 2018

Hou, Kevin J.; Qin, Jian
Macromolecules, Vol. 51, Issue 19
DOI: 10.1021/acs.macromol.8b01616

Morphologies of block copolymers composed of charged and neutral blocks
journal, January 2012

Wang, Xiaojun; Goswami, Monojoy; Kumar, Rajeev
Soft Matter, Vol. 8, Issue 11
DOI: 10.1039/c2sm07223h

A Perspective on the Design of Ion-Containing Polymers for Polymer Electrolyte Applications
journal, February 2021

Ma, Boran; Olvera de la Cruz, Monica
The Journal of Physical Chemistry B, Vol. 125, Issue 12
DOI: 10.1021/acs.jpcb.0c08707

Phase Behavior of Melts of Diblock-Copolymers with One Charged Block
journal, June 2019

Gavrilov, Alexey A.; Chertovich, Alexander V.; Potemkin, Igor I.
Polymers, Vol. 11, Issue 6
DOI: 10.3390/polym11061027

Similar Records in DOE PAGES and OSTI.GOV collections:

Self-Assembly of Partially Charged Diblock Copolymer-Homopolymer Ternary Blends

Journal Article Zheng, Caini ; Zhang, Bo ; Bates, Frank S. ; ... - Macromolecules

Ternary blends comprising a diblock copolymer and the corresponding homopolymers provide ready access to a variety of morphologies, but the impact of charge on their phase behavior has not been studied extensively. Here, three partially charged ternary blends consisting of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)] (POEGMA#), polystyrene (PS), and POEGMA#-PS with different charge fractions were prepared, where # denotes the mole fraction of charged monomers in the POEGMA chain. The phase behavior was systematically studied using small-angle X-ray scattering, and isothermal phase diagrams at 120 °C were constructed. The resulting isothermal planes contain amore »« less
https://doi.org/10.1021/acs.macromol.2c00518

Full Text Available
Superlattice by charged block copolymer self-assembly

Journal Article Shim, Jimin ; Bates, Frank S. ; Lodge, Timothy P. - Nature Communications

Charged block copolymers are of great interest due to their unique self-assembly and physicochemical properties. Understanding of the phase behavior of charged block copolymers, however, is still at a primitive stage. Here we report the discovery of an intriguing superlattice morphology from compositionally symmetric charged block copolymers, poly[(oligo(ethylene glycol) methyl ether methacrylate–co–oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]–b–polystyrene (POEGMA–PS), achieved by systematic variation of the molecular structure in general, and the charge content in particular. POEGMA–PS self-assembles into a superlattice lamellar morphology, a previously unknown class of diblock nanostructures, but strikingly similar to oxygen-deficient perovskite derivatives, when the fraction of chargedmore »« less
Cited by 34
https://doi.org/10.1038/s41467-019-10141-z

Full Text Available
Phase structures and morphologies determined by competitions among self-organization, crystallization, and vitrification in a disordered poly(ethylene oxide)-{ital b}-polystyrene diblock copolymer

Journal Article Zhu, L ; Chen, Y ; Zhang, A ; ... - Physical Review, B: Condensed Matter

A poly(ethylene oxide)-{ital b}-polystyrene (PEO-{ital b}-PS) diblock copolymer having a number-average molecular weight ({bar M}{sub n}) of 11&hthinsp;000 g/mol in the PEO blocks and an {bar M}{sub n} of 5200 g/mol in the PS blocks has been synthesized (with a volume fraction of the PEO blocks of 0.66 in the molten state). Differential scanning calorimetry results show that this copolymer possesses a single endotherm, which is attributed to the melting of the PEO-block crystals. Based on real-time resolved synchrotron small-angle x-ray scattering (SAXS) observations, the diblock copolymer is in a disordered state above the glass transition temperature of the PS-richmore »« less
https://doi.org/10.1103/PhysRevB.60.10022
Effect of Ion Concentration on the Formation of Bicontinuous Microemulsions in Partially Charged Ternary Polymer Blends

Journal Article Shim, Jimin ; Xie, Shuyi ; Bates, Frank S. ; ... - Macromolecules

We describe the formation of bicontinuous microemulsions (BμE) from a series of three model charged ternary polymer blends comprising an AB diblock copolymer and the constituent A and B homopolymers, where A is a partially charged poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)] (POEGMA) block with systematically tuned ion concentration and B is a neutral polystyrene (PS) block. The mole fraction of charged groups in the POEGMA block and the corresponding POEGMA homopolymer was 7, 23, or 36%. The phase diagrams of ternary blends with variable ion concentrations have been mapped out along the volumetrically symmetric isoplethmore »« less
Cited by 5
https://doi.org/10.1021/acs.macromol.9b02104

Full Text Available
Effect of Added Salt on Disordered Poly(ethylene oxide)-Block-Poly(methyl methacrylate) Copolymer Electrolytes

Journal Article Shah, Neel J. ; Dadashi-Silab, Sajjad ; Galluzzo, Michael D. ; ... - Macromolecules

In this report we studied the effect of salt addition on a diblock copolymer system with a negative Flory-Huggins interaction parameter, χ, indicative of attractive interactions between the two blocks. The system studied is poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-PMMA) with added lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. We studied two asymmetric block copolymers, PEO-PMMA(10-33) and PEO-PMMA(10-64), where the numbers refer to the molar masses of the blocks in kg mol^-1. The small-angle X-ray scattering (SAXS) profiles for PEO-PMMA(10-33) were featureless at all salt concentrations. In contrast, PEO-PMMA(10-64) exhibited SAXS peaks when the salt concentration was between 0.22 ≤ m (mol Li/kg polymer) ≤more »« less
https://doi.org/10.1021/acs.macromol.0c02493

Full Text Available

Similar Records

Title: Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

Abstract

Citation Formats

Effect of Lithium-Ion Concentration on Morphology and Ion Transport in Single-Ion-Conducting Block Copolymer Electrolytes journal, September 2015

Microphase separation of charged diblock copolymers: melts and solutions journal, September 1992

Anomalous Phase Behavior of Ionic Polymer Blends and Ionic Copolymers journal, June 2017

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

Fluctuation effects in the theory of microphase separation in block copolymers journal, July 1987

Synthesis and Surface Characterization of Well-Defined Amphiphilic Block Copolymers Containing Poly[oligo(ethylene glycol) methacrylate] Segments journal, January 2006

Ion-Complexation-Induced Changes in the Interaction Parameter and the Chain Conformation of PS- b -PMMA Copolymers journal, July 2008

Issues and challenges facing rechargeable lithium batteries journal, November 2001

Ionic Conduction and Dielectric Response of Poly(imidazolium acrylate) Ionomers journal, April 2012

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups journal, June 2015

Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts journal, April 2012

Theory of Microphase Separation in Block Copolymers journal, November 1980

Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity journal, January 2015

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

Role of Tethered Ion Placement on Polymerized Ionic Liquid Structure and Conductivity: Pendant versus Backbone Charge Placement journal, July 2016

Influence of Bound Ion on the Morphology and Conductivity of Anion-Conducting Block Copolymers journal, February 2013

Thermodynamics of Salt-Doped Block Copolymers journal, July 2014

Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries journal, January 2001

Polymer Electrolytes journal, July 2013

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

Block Copolymer Thermodynamics: Theory and Experiment journal, October 1990

Self-assembly in block polyelectrolytes journal, February 2011

Prediction of polymer densities journal, May 1969

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives journal, January 2017

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

Effect of Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers journal, July 2011

Block Copolymers—Designer Soft Materials journal, February 1999

Theory of Solutions of High Polymers 1 journal, July 1942

Anhydrous Proton Transport in Polymerized Ionic Liquid Block Copolymers: Roles of Block Length, Ionic Content, and Confinement journal, December 2015

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt journal, August 2018

Network Structure and Strong Microphase Separation for High Ion Conductivity in Polymerized Ionic Liquid Block Copolymers journal, June 2013

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

Molecular Mobility and Cation Conduction in Polyether–Ester–Sulfonate Copolymer Ionomers journal, April 2012

Thermodynamics of High Polymer Solutions journal, January 1942

Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study journal, December 2011

Microphase separation in polyelectrolytic diblock copolymer melt: Weak segregation limit journal, June 2007

Single‐Ion Conducting Polymer Electrolytes for Solid‐State Lithium–Metal Batteries: Design, Performance, and Challenges journal, February 2021

Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries journal, May 2014

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations journal, June 2016

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

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

Impact of Electrostatic Interactions on the Self-Assembly of Charge-Neutral Block Copolyelectrolytes journal, January 2020

Polyelectrolyte Blends and Nontrivial Behavior in Effective Flory–Huggins Parameters journal, July 2014

Phase Behavior and Block Sequence Effects in Lithium Perchlorate-Doped Poly(isoprene- b -styrene- b -ethylene oxide) and Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymers journal, April 2003

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers journal, February 2019

Physical Properties of Polymers Handbook book, January 2007

Self-Assembly of Charge-Containing Copolymers at the Liquid–Liquid Interface journal, March 2019

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

Phase Behavior of Symmetric Sulfonated Block Copolymers journal, May 2008

Superlattice by charged block copolymer self-assembly journal, May 2019

Segmental Dynamics of Ethylene Oxide-Containing Polymers with Diverse Backbone Chemistries journal, February 2016

Phase Behavior and Ionic Conductivity of Lithium Perchlorate-Doped Polystyrene- b -poly(2-vinylpyridine) Copolymer journal, August 2011

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation journal, May 2020

Electrostatic control of block copolymer morphology journal, June 2014

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

Thermodynamics of Block Copolymers with and without Salt journal, December 2013

Lithium battery chemistries enabled by solid-state electrolytes journal, February 2017

Solvation and Entropic Regimes in Ion-Containing Block Copolymers journal, September 2018

Morphologies of block copolymers composed of charged and neutral blocks journal, January 2012

A Perspective on the Design of Ion-Containing Polymers for Polymer Electrolyte Applications journal, February 2021

Phase Behavior of Melts of Diblock-Copolymers with One Charged Block journal, June 2019

Effect of Lithium-Ion Concentration on Morphology and Ion Transport in Single-Ion-Conducting Block Copolymer Electrolytes
journal, September 2015

Microphase separation of charged diblock copolymers: melts and solutions
journal, September 1992

Anomalous Phase Behavior of Ionic Polymer Blends and Ionic Copolymers
journal, June 2017

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

Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

Synthesis and Surface Characterization of Well-Defined Amphiphilic Block Copolymers Containing Poly[oligo(ethylene glycol) methacrylate] Segments
journal, January 2006

Ion-Complexation-Induced Changes in the Interaction Parameter and the Chain Conformation of PS- b -PMMA Copolymers
journal, July 2008

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

Ionic Conduction and Dielectric Response of Poly(imidazolium acrylate) Ionomers
journal, April 2012

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups
journal, June 2015

Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts
journal, April 2012

Theory of Microphase Separation in Block Copolymers
journal, November 1980

Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity
journal, January 2015

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

Role of Tethered Ion Placement on Polymerized Ionic Liquid Structure and Conductivity: Pendant versus Backbone Charge Placement
journal, July 2016

Influence of Bound Ion on the Morphology and Conductivity of Anion-Conducting Block Copolymers
journal, February 2013

Thermodynamics of Salt-Doped Block Copolymers
journal, July 2014

Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries
journal, January 2001

Polymer Electrolytes
journal, July 2013

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

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990

Self-assembly in block polyelectrolytes
journal, February 2011

Prediction of polymer densities
journal, May 1969

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives
journal, January 2017

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

Effect of Nanoscale Morphology on the Conductivity of Polymerized Ionic Liquid Block Copolymers
journal, July 2011

Block Copolymers—Designer Soft Materials
journal, February 1999

Theory of Solutions of High Polymers ¹
journal, July 1942

Anhydrous Proton Transport in Polymerized Ionic Liquid Block Copolymers: Roles of Block Length, Ionic Content, and Confinement
journal, December 2015

Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt
journal, August 2018

Network Structure and Strong Microphase Separation for High Ion Conductivity in Polymerized Ionic Liquid Block Copolymers
journal, June 2013

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

Molecular Mobility and Cation Conduction in Polyether–Ester–Sulfonate Copolymer Ionomers
journal, April 2012

Thermodynamics of High Polymer Solutions
journal, January 1942

Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study
journal, December 2011

Microphase separation in polyelectrolytic diblock copolymer melt: Weak segregation limit
journal, June 2007

Single‐Ion Conducting Polymer Electrolytes for Solid‐State Lithium–Metal Batteries: Design, Performance, and Challenges
journal, February 2021

Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries
journal, May 2014

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations
journal, June 2016

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

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

Impact of Electrostatic Interactions on the Self-Assembly of Charge-Neutral Block Copolyelectrolytes
journal, January 2020

Polyelectrolyte Blends and Nontrivial Behavior in Effective Flory–Huggins Parameters
journal, July 2014

Phase Behavior and Block Sequence Effects in Lithium Perchlorate-Doped Poly(isoprene- b -styrene- b -ethylene oxide) and Poly(styrene- b -isoprene- b -ethylene oxide) Triblock Copolymers
journal, April 2003

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers
journal, February 2019

Physical Properties of Polymers Handbook
book, January 2007

Self-Assembly of Charge-Containing Copolymers at the Liquid–Liquid Interface
journal, March 2019

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

Phase Behavior of Symmetric Sulfonated Block Copolymers
journal, May 2008

Superlattice by charged block copolymer self-assembly
journal, May 2019

Segmental Dynamics of Ethylene Oxide-Containing Polymers with Diverse Backbone Chemistries
journal, February 2016

Phase Behavior and Ionic Conductivity of Lithium Perchlorate-Doped Polystyrene- b -poly(2-vinylpyridine) Copolymer
journal, August 2011

Comparing Experimental Phase Behavior of Ion-Doped Block Copolymers with Theoretical Predictions Based on Selective Ion Solvation
journal, May 2020

Electrostatic control of block copolymer morphology
journal, June 2014

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

Thermodynamics of Block Copolymers with and without Salt
journal, December 2013

Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017

Solvation and Entropic Regimes in Ion-Containing Block Copolymers
journal, September 2018

Morphologies of block copolymers composed of charged and neutral blocks
journal, January 2012

A Perspective on the Design of Ion-Containing Polymers for Polymer Electrolyte Applications
journal, February 2021

Phase Behavior of Melts of Diblock-Copolymers with One Charged Block
journal, June 2019