Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

Li, Xiuhong; Loo, Whitney S.; Jiang, Xi; Wang, Xin; Galluzzo, Michael D.; Mongcopa, Katrina I.; Wang, Andrew A.; Balsara, Nitash P.; Garetz, Bruce A.

doi:10.1021/acs.macromol.8b02142

Title: Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

Journal Article · Wed Jan 23 00:00:00 EST 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.8b02142· OSTI ID:1594908

Li, Xiuhong ^[1];

^[2];

^[3]; Wang, Xin ^[1]; Galluzzo, Michael D. ^[4];

^[2]; Wang, Andrew A. ^[2];

^[4];

^[1]

New York Univ. (NYU), NY (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

In this work, crystallization in an ordered lamellar diblock copolymer/salt mixture, polystyrene-block-poly(ethylene oxide) mixed with lithium bis(trifluoromethanesulfonyl)imide salt (SEO/LiTFSI), has been studied using a combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and depolarized light scattering (DPLS). Such materials have applications as electrolyte membranes in solid-state lithium batteries. The grain structure of the electrolyte was controlled by manipulating thermal history. Poly(ethylene oxide) (PEO) crystallization was confined within the microphase-separated morphology and did not affect the grain structure in the case of shallow quenches. Deep quenches resulted in unconfined crystallization, where crystal formation does not affect the microphase-separated morphology but does alter the grain structure. The difference between the two modes of crystallization can only be detected by DPLS. This knowledge is particularly relevant for nanostructured electrolytes wherein ion transport is a strong function of grain structure.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231; DMR-1505476; DMR-1505444; AC02-76SF00515; DGE-1106400

OSTI ID:: 1594908

Journal Information:: Macromolecules, Vol. 52, Issue 3; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

References (47)

Morphology of semicrystalline block copolymers of ethylene-(ethylene-alt-propylene) Rangarajan, Pratima; Register, Richard A.; Fetters, Lewis J. Macromolecules, Vol. 26, Issue 17 https://doi.org/10.1021/ma00069a034	journal	August 1993
Phase structures and morphologies determined by self-organization, vitrification, and crystallization: confined crystallization in an ordered lamellar phase of PEO-b-PS diblock copolymer Zhu, L.; Cheng, S. Z. D.; Calhoun, B. H. Polymer, Vol. 42, Issue 13 https://doi.org/10.1016/S0032-3861(00)00902-2	journal	June 2001
Crystallization Behavior of Crystalline‐Amorphous Diblock Copolymers Consisting of a Rubbery Amorphous Block Nandan, Bhanu; Hsu, Jen‐Yung; Chen, Hsin‐Lung Journal of Macromolecular Science, Part C: Polymer Reviews, Vol. 46, Issue 2 https://doi.org/10.1080/15321790600646802	journal	September 2006
Crystallization assisted self-assembly of semicrystalline block copolymers He, Wei-Na; Xu, Jun-Ting Progress in Polymer Science, Vol. 37, Issue 10 https://doi.org/10.1016/j.progpolymsci.2012.05.002	journal	October 2012
Crystallization of tethered polyethylene in confined geometries Weimann, P. A.; Hajduk, D. A.; Chu, C. Journal of Polymer Science Part B: Polymer Physics, Vol. 37, Issue 16 https://doi.org/10.1002/(SICI)1099-0488(19990815)37:16<2053::AID-POLB9>3.0.CO;2-L	journal	August 1999
Direct imaging of polyethylene crystallites within block copolymer microdomains Loo, Yueh-Lin; Register, Richard A.; Adamson, Douglas H. Journal of Polymer Science Part B: Polymer Physics, Vol. 38, Issue 19 https://doi.org/10.1002/1099-0488(20001001)38:19<2564::AID-POLB80>3.0.CO;2-Y	journal	January 2000
Confined Crystallization of Ethylene Oxide−Butadiene Diblock Copolymers in Lamellar Films Opitz, Ricarda; Lambreva, Denitza M.; de Jeu, Wim H. Macromolecules, Vol. 35, Issue 18 https://doi.org/10.1021/ma020373f	journal	August 2002
Crystallization of a Weakly Segregated Polyolefin Diblock Copolymer Rangarajan, Pratima; Register, Richard A.; Fetters, Lewis J. Macromolecules, Vol. 28, Issue 14 https://doi.org/10.1021/ma00118a022	journal	July 1995
Structure Development in Semicrystalline Diblock Copolymers Crystallizing from the Ordered Melt Ryan, A. J.; Hamley, I. W.; Bras, W. Macromolecules, Vol. 28, Issue 11 https://doi.org/10.1021/ma00115a016	journal	May 1995
Ordering Dynamics of Compositionally Asymmetric Styrene−Isoprene Block Copolymers Adams, J. LaMonte; Quiram, Daniel J.; Graessley, William W. Macromolecules, Vol. 29, Issue 8 https://doi.org/10.1021/ma951261+	journal	January 1996
Crystallization of Asymmetric Diblock Copolymers from Microphase-Separated Melts Quiram, Daniel J.; Register, Richard A.; Marchand, Gary R. Macromolecules, Vol. 30, Issue 16 https://doi.org/10.1021/ma961524f	journal	August 1997
Modes of Crystallization in Block Copolymer Microdomains: Breakout, Templated, and Confined Loo, Yueh-Lin; Register, Richard A.; Ryan, Anthony J. Macromolecules, Vol. 35, Issue 6 https://doi.org/10.1021/ma011824j	journal	March 2002
Growth of Grains and Correlated Grain Clusters in a Block Copolymer Melt Newstein, M. C.; Garetz, B. A.; Balsara, N. P. Macromolecules, Vol. 31, Issue 1 https://doi.org/10.1021/ma971086s	journal	January 1998
Role of Grain Boundary Defects During Grain Coarsening of Lamellar Block Copolymers Ryu, Hyung Ju; Fortner, David B.; Lee, Sukbin Macromolecules, Vol. 46, Issue 1 https://doi.org/10.1021/ma3015382	journal	December 2012
Retardation of Grain Growth and Grain Boundary Pinning in Athermal Block Copolymer Blend Systems Ryu, Hyung Ju; Sun, Jane; Avgeropoulos, Apostolos Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma4021714	journal	February 2014
Measurement of Gyroid Single Grain Growth Rates in Block Copolymer Solutions Chastek, Thomas Q.; Lodge, Timothy P. Macromolecules, Vol. 36, Issue 20 https://doi.org/10.1021/ma034833w	journal	September 2003
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
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
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
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
Effect of Crystallization on Proton Transport in Model Polymer Electrolyte Membranes Beers, Keith M.; Wong, David T.; Jackson, Andrew J. Macromolecules, Vol. 47, Issue 13 https://doi.org/10.1021/ma500298w	journal	June 2014
Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi Macromolecules, Vol. 49, Issue 18 https://doi.org/10.1021/acs.macromol.6b01553	journal	September 2016
Simulation of local ion transport in lamellar block copolymer electrolytes based on electron micrographs Chintapalli, Mahati; Higa, Kenneth; Chen, X. Chelsea Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 3 https://doi.org/10.1002/polb.24268	journal	December 2016
The influence of phase segregation on properties of semicrystalline PEO:LiTFSI electrolytes Marzantowicz, M.; Krok, F.; Dygas, J. R. Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2007.11.035	journal	September 2008
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
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
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
Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes Yuan, Rodger; Teran, Alexander A.; Gurevitch, Inna Macromolecules, Vol. 46, Issue 3 https://doi.org/10.1021/ma3024552	journal	January 2013
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
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes Sethi, Gurmukh K.; Jiang, Xi; Chakraborty, Rohan ACS Macro Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsmacrolett.8b00583	journal	August 2018
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
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
Differential scanning calorimetry studies on poly(ethylene glycol) with different molecular weights for thermal energy storage materials Pielichowski, Krzysztof; Flejtuch, Kinga Polymers for Advanced Technologies, Vol. 13, Issue 10-12 https://doi.org/10.1002/pat.276	journal	October 2002
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
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
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
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
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
Dynamics of Structure Formation and Crystallization in Asymmetric Diblock Copolymers Quiram, Daniel J.; Register, Richard A.; Marchand, Gary R. Macromolecules, Vol. 30, Issue 26 https://doi.org/10.1021/ma9708050	journal	December 1997
Anisotropy of lamellar block copolymer grains Balsara, N. P.; Marques, C. M.; Garetz, B. A. Physical Review E, Vol. 66, Issue 5 https://doi.org/10.1103/PhysRevE.66.052802	journal	November 2002
Grain shapes and growth kinetics during self-assembly of block copolymers Chastek, Thomas Q.; Lodge, Timothy P. Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 3 https://doi.org/10.1002/polb.20718	journal	January 2005
Twinning and growth kinetics of lamellar grains in a diblock copolymer solution Chastek, Thomas Q.; Lodge, Timothy P. Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 4 https://doi.org/10.1002/polb.20336	journal	January 2005
Ordering Dynamics of a Symmetric Polystyrene- block -polyisoprene. 1. Ordering Mechanism from the Disordered State Sakamoto, Naoki; Hashimoto, Takeji Macromolecules, Vol. 31, Issue 10 https://doi.org/10.1021/ma9717202	journal	May 1998
Birefringence and diffraction of light in ordered block copolymer materials Garetz, B. A.; Newstein, M. C.; Dai, H. J. Macromolecules, Vol. 26, Issue 12 https://doi.org/10.1021/ma00064a026	journal	June 1993
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes Lascaud, S.; Perrier, M.; Vallee, A. Macromolecules, Vol. 27, Issue 25 https://doi.org/10.1021/ma00103a034	journal	December 1994
Correlations between Salt-Induced Crystallization, Morphology, Segmental Dynamics, and Conductivity in Amorphous Block Copolymer Electrolytes Thelen, Jacob L.; Wang, Andrew A.; Chen, X. Chelsea Macromolecules, Vol. 51, Issue 5 https://doi.org/10.1021/acs.macromol.7b02415	journal	February 2018

Cited By (1)

Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B. The Journal of Chemical Physics, Vol. 151, Issue 2 https://doi.org/10.1063/1.5109684	journal	July 2019

Similar Records

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

Journal Article · Fri Feb 26 00:00:00 EST 2016 · Macromolecules · OSTI ID:1594908

Chintapalli, Mahati; Le, Thao N. P.; Venkatesan, Naveen R.; +6 more

Correlations between Salt-Induced Crystallization, Morphology, Segmental Dynamics, and Conductivity in Amorphous Block Copolymer Electrolytes

Journal Article · Tue Feb 20 00:00:00 EST 2018 · Macromolecules · OSTI ID:1594908

Thelen, Jacob L.; Wang, Andrew A.; Chen, X. Chelsea; +3 more

Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Journal Article · Thu Jun 04 00:00:00 EDT 2020 · ACS Nano · OSTI ID:1594908

Sharon, Daniel; Bennington, Peter; Dolejsi, Moshe; +5 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Scattering
Grain
Crystallization
Crystal structure
X-ray scattering

Title: Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

Citation Formats

References (47)

Cited By (1)

Similar Records

Related Subjects