Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt

Loo, Whitney S.; Galluzzo, Michael D.; Li, Xiuhong; Maslyn, Jacqueline A.; Oh, Hee Jeung; Mongcopa, Katrina I.; Zhu, Chenhui; Wang, Andrew A.; Wang, Xin; Garetz, Bruce A.; Balsara, Nitash P.

doi:10.1021/acs.jpcb.8b04189

Title: Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt

Journal Article · Wed Aug 01 00:00:00 EDT 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.8b04189· OSTI ID:1605219

^[1]; Galluzzo, Michael D. ^[2]; Li, Xiuhong ^[3];

^[2]; Oh, Hee Jeung ^[1];

^[1]; Zhu, Chenhui ^[4]; Wang, Andrew A. ^[1]; Wang, Xin ^[5];

^[3];

^[6]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
New York Univ. (NYU), Brooklyn, NY (United States). Tandon School of Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
New York Univ. (NYU), Brooklyn, NY (United States). Tandon School of Engineering
Univ. of California, Berkeley, CA (United States); New York Univ. (NYU), Brooklyn, NY (United States). Tandon School of Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

We present experimental results on the phase behavior of block copolymer/salt mixtures over a wide range of copolymer compositions, molecular weights, and salt concentrations. The experimental system comprises polystyrene-block-poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. It is well established that LiTFSI interacts favorably with poly(ethylene oxide) relative to polystyrene. The relationship between chain length and copolymer composition at fixed temperature is U-shaped, as seen in experiments on conventional block copolymers and as anticipated from the standard self-consistent field theory (SCFT) of block copolymer melts. The phase behavior can be explained in terms of an effective Flory-Huggins interaction parameter between the polystyrene monomers and poly(ethylene oxide) monomers complexed with the salt, χ_eff, which increases linearly with salt concentration. The phase behavior of salt-containing block copolymers, plotted on a segregation strength versus copolymer composition plot, is similar to that of conventional (uncharged) block copolymer melts, when the parameter χ_eff replaces χ in segregation strength.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1605219

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 122, Issue 33; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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References (50)

Rubbery Block Copolymer Electrolytes for Solid-State Rechargeable Lithium Batteries Soo, Philip P. Journal of The Electrochemical Society, Vol. 146, Issue 1 https://doi.org/10.1149/1.1391560	journal	January 1999
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
Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes Singh, Mohit; Odusanya, Omolola; Wilmes, Gregg M. Macromolecules, Vol. 40, Issue 13 https://doi.org/10.1021/ma0629541	journal	June 2007
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes Pesko, Danielle M.; Timachova, Ksenia; Bhattacharya, Rajashree Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0581711jes	journal	January 2017
Block Copolymer Thermodynamics: Theory and Experiment Bates, Frank S.; Fredrickson, Glenn H. Annual Review of Physical Chemistry, Vol. 41, Issue 1 https://doi.org/10.1146/annurev.pc.41.100190.002521	journal	October 1990
Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation Cochran, Eric W.; Garcia-Cervera, Carlos J.; Fredrickson, Glenn H. Macromolecules, Vol. 39, Issue 7 https://doi.org/10.1021/ma0527707	journal	April 2006
Equilibrium morphology of block copolymer melts. 3 Kawasaki, Kyozi; Kawakatsu, Toshihiro Macromolecules, Vol. 23, Issue 17 https://doi.org/10.1021/ma00219a022	journal	August 1990
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Thermodynamics of Block Copolymers with and without Salt Teran, Alexander A.; Balsara, Nitash P. The Journal of Physical Chemistry B, Vol. 118, Issue 1 https://doi.org/10.1021/jp408079z	journal	December 2013
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 Epps, Thomas H.; Bailey, Travis S.; Waletzko, Ryan Macromolecules, Vol. 36, Issue 8 https://doi.org/10.1021/ma021231o	journal	April 2003
Lithium Salt-Induced Microstructure and Ordering in Diblock Copolymer/Homopolymer Blends Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi Macromolecules, Vol. 49, Issue 13 https://doi.org/10.1021/acs.macromol.6b00995	journal	June 2016
Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study Gunkel, Ilja; Thurn-Albrecht, Thomas Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma201334h	journal	December 2011
Thermodynamic Properties of Block Copolymer Electrolytes Containing Imidazolium and Lithium Salts Wanakule, Nisita S.; Virgili, Justin M.; Teran, Alexander A. Macromolecules, Vol. 43, Issue 19 https://doi.org/10.1021/ma1013786	journal	October 2010
Salt-doped block copolymers: ion distribution, domain spacing and effective χ parameter Nakamura, Issei; Wang, Zhen-Gang Soft Matter, Vol. 8, Issue 36 https://doi.org/10.1039/c2sm25606a	journal	January 2012
Polyelectrolyte Blends and Nontrivial Behavior in Effective Flory–Huggins Parameters Sing, Charles E.; Olvera de la Cruz, Monica ACS Macro Letters, Vol. 3, Issue 8 https://doi.org/10.1021/mz500202n	journal	July 2014
Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes Ganesan, Venkat; Pyramitsyn, Victor; Bertoni, Colleen ACS Macro Letters, Vol. 1, Issue 4 https://doi.org/10.1021/mz300051x	journal	March 2012
Ion Correlation Effects in Salt-Doped Block Copolymers Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M. Physical Review Letters, Vol. 120, Issue 12 https://doi.org/10.1103/PhysRevLett.120.127801	journal	March 2018
Ordering Transition in Salt-Doped Diblock Copolymers Qin, Jian; de Pablo, Juan J. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.5b02643	journal	April 2016
Effects of Ion Solvation on the Miscibility of Binary Polymer Blends ^† Wang, Zhen-Gang The Journal of Physical Chemistry B, Vol. 112, Issue 50 https://doi.org/10.1021/jp806897t	journal	December 2008
Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries Ruzette, Anne-Valérie G.; Soo, Philip P.; Sadoway, Donald R. Journal of The Electrochemical Society, Vol. 148, Issue 6 https://doi.org/10.1149/1.1368097	journal	January 2001
Effects of Ion-Induced Cross-Linking on the Phase Behavior in Salt-Doped Polymer Blends Ren, Chun-Lai; Nakamura, Issei; Wang, Zhen-Gang Macromolecules, Vol. 49, Issue 1 https://doi.org/10.1021/acs.macromol.5b02229	journal	December 2015
Ion Correlation-Induced Phase Separation in Polyelectrolyte Blends Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica ACS Macro Letters, Vol. 2, Issue 11 https://doi.org/10.1021/mz400511r	journal	November 2013
Electrostatic control of block copolymer morphology Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica Nature Materials, Vol. 13, Issue 7 https://doi.org/10.1038/nmat4001	journal	June 2014
Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity Sing, Charles E.; Zwanikken, Jos W.; de la Cruz, Monica Olvera The Journal of Chemical Physics, Vol. 142, Issue 3 https://doi.org/10.1063/1.4905830	journal	January 2015
Anomalous Phase Behavior of Ionic Polymer Blends and Ionic Copolymers Pryamitsyn, Victor A.; Kwon, Ha-Kyung; Zwanikken, Jos W. Macromolecules, Vol. 50, Issue 13 https://doi.org/10.1021/acs.macromol.7b00523	journal	June 2017
Anionic polymerization: High vacuum techniques Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18 https://doi.org/10.1002/1099-0518(20000915)38:18<3211::AID-POLA10>3.0.CO;2-L	journal	January 2000
Relationship between Conductivity, Ion Diffusion, and Transference Number in Perfluoropolyether Electrolytes Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.6b00412	journal	April 2016
Phase Behavior of a Block Copolymer/Salt Mixture through the Order-to-Disorder Transition Thelen, Jacob L.; Teran, Alexander A.; Wang, Xin Macromolecules, Vol. 47, Issue 8 https://doi.org/10.1021/ma500292n	journal	April 2014
Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes Gomez, Enrique D.; Panday, Ashoutosh; Feng, Edward H. Nano Letters, Vol. 9, Issue 3 https://doi.org/10.1021/nl900091n	journal	March 2009
Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling Gilbert, Jonathan B.; Luo, Ming; Shelton, Cameron K. ACS Nano, Vol. 9, Issue 1 https://doi.org/10.1021/nn505744r	journal	December 2014
Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers Gartner, Thomas E.; Morris, Melody A.; Shelton, Cameron K. Macromolecules, Vol. 51, Issue 5 https://doi.org/10.1021/acs.macromol.7b02600	journal	February 2018
Reentrant phase behavior and coexistence in asymmetric block copolymer electrolytes Loo, Whitney S.; Jiang, Xi; Maslyn, Jacqueline A. Soft Matter, Vol. 14, Issue 15 https://doi.org/10.1039/C8SM00175H	journal	January 2018
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator Hexemer, Alexander; Bras, Wim; Glossinger, James Journal of Physics: Conference Series, Vol. 247 https://doi.org/10.1088/1742-6596/247/1/012007	journal	October 2010
Characterization of a Block Copolymer with a Wide Distribution of Grain Sizes Wang, Xin; Chintapalli, Mahati; Newstein, Maurice C. Macromolecules, Vol. 49, Issue 21 https://doi.org/10.1021/acs.macromol.6b01380	journal	October 2016
Depolarized Scattering from Block Copolymer Grains Using Circularly Polarized Light Wang, Xin; Li, Xiuhong; Loo, Whitney Macromolecules, Vol. 50, Issue 13 https://doi.org/10.1021/acs.macromol.7b01048	journal	June 2017
Birefringence detection of the order-to-disorder transition in block copolymer liquids Balsara, N. P.; Perahia, D.; Safinya, C. R. Macromolecules, Vol. 25, Issue 15 https://doi.org/10.1021/ma00041a011	journal	July 1992
First-Order Disordered-to-Lamellar Phase Transition in Lithium Salt-Doped Block Copolymers Nakamura, Issei; Balsara, Nitash P.; Wang, Zhen-Gang ACS Macro Letters, Vol. 2, Issue 6 https://doi.org/10.1021/mz4001404	journal	May 2013
Evolution of Grain Structure during Disorder-to-Order Transitions in a Block Copolymer/Salt Mixture Studied by Depolarized Light Scattering Wang, Xin; Thelen, Jacob L.; Teran, Alexander A. Macromolecules, Vol. 47, Issue 16 https://doi.org/10.1021/ma501166p	journal	August 2014
Order−Disorder Transition in Poly(oxyethylene)−Poly(oxybutylene) Diblock Copolymers Mai, Shao-Min; Fairclough, J. Patrick A.; Hamley, Ian W. Macromolecules, Vol. 29, Issue 19 https://doi.org/10.1021/ma960105f	journal	January 1996
Discontinuous Changes in Ionic Conductivity of a Block Copolymer Electrolyte through an Order–Disorder Transition Teran, Alexander A.; Mullin, Scott A.; Hallinan, Daniel T. ACS Macro Letters, Vol. 1, Issue 2 https://doi.org/10.1021/mz200183t	journal	January 2012
Relationship between birefringence and the structure of ordered block copolymer materials Balsara, N. P.; Garetz, B. A.; Dai, H. J. Macromolecules, Vol. 25, Issue 22 https://doi.org/10.1021/ma00048a036	journal	October 1992
Renormalization of the one-loop theory of fluctuations in polymer blends and diblock copolymer melts Grzywacz, Piotr; Qin, Jian; Morse, David C. Physical Review E, Vol. 76, Issue 6 https://doi.org/10.1103/PhysRevE.76.061802	journal	December 2007
Renormalized one-loop theory of correlations in polymer blends Qin, Jian; Morse, David C. The Journal of Chemical Physics, Vol. 130, Issue 22 https://doi.org/10.1063/1.3124799	journal	June 2009
Critical Point of Symmetric Binary Homopolymer Blends Spencer, Russell K. W.; Matsen, Mark W. Macromolecules, Vol. 49, Issue 16 https://doi.org/10.1021/acs.macromol.6b01437	journal	August 2016
50th Anniversary Perspective : Phase Behavior of Polymer Solutions and Blends Knychała, Piotr; Timachova, Ksenia; Banaszak, Michał Macromolecules, Vol. 50, Issue 8 https://doi.org/10.1021/acs.macromol.6b02619	journal	April 2017
Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit Chintapalli, Mahati; Le, Thao N. P.; Venkatesan, Naveen R. Macromolecules, Vol. 49, Issue 5 https://doi.org/10.1021/acs.macromol.5b02620	journal	February 2016
Phase Equilibria in Polymer—Solvent Systems ^1,2 Shultz, A. R.; Flory, P. J. Journal of the American Chemical Society, Vol. 74, Issue 19 https://doi.org/10.1021/ja01139a010	journal	October 1952
Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: Applicability of an extended flory–huggins equation Bae, Y. C.; Shim, J. J.; Soane, D. S. Journal of Applied Polymer Science, Vol. 47, Issue 7 https://doi.org/10.1002/app.1993.070470707	journal	February 1993
Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S. Macromolecules, Vol. 28, Issue 26 https://doi.org/10.1021/ma00130a012	journal	December 1995

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt

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