Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

Sethi, Gurmukh K.; Jung, Ha Young; Loo, Whitney S.; Sawhney, Simar; Park, Moon Jeong; Balsara, Nitash P.; Villaluenga, Irune

doi:10.1021/acs.macromol.9b00042

Title: Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

Journal Article · Wed Apr 17 00:00:00 EDT 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.9b00042· OSTI ID:1604684

^[1]; Jung, Ha Young ^[2];

^[3]; Sawhney, Simar ^[3];

^[2];

^[1];

^[4]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Pohang Univ. of Science and Technology (POSTECH) (Korea)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

© 2019 American Chemical Society. We examine the phase behavior of a hybrid organic-inorganic diblock copolymer/salt mixtures. The experimental system comprises poly(ethylene oxide)-block-polyhedral oligomeric silsesquioxane (PEO-POSS) mixed with a lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) salt. Although the diblock copolymers without salt exhibit a classical order-to-disorder transition behavior with increasing temperature, the PEO-POSS/salt mixtures exhibit disorder-to-order transitions with increasing temperature. The analysis of a small-angle X-ray scattering data from the disordered state using Leibler's random phase approximation enables the determination of an effective Flory-Huggins interaction parameter, χ_eff , for the electrolytes. Unlike conventional systems, χ_eff increases with increasing temperature. A simple expression is proposed to describe the dependence of χ_eff on temperature and salt concentration. This enables the calculation of the segregation strength, χ_effN, for both ordered and disordered electrolytes. The composition of the electrolytes is quantified by f_EO/LiTFSI , the volume fraction of the salt-containing poly(ethylene oxide)-rich phase. The morphology of electrolytes is presented on a χ eff N versus f_EO/LiTFSI phase diagram. Finally, over the values of f_EO/LiTFSI studied (0.61-0.91), only two ordered phases were found: lamellae and co-existing lamellae/hexagonally packed cylinders.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

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

OSTI ID:: 1604684

Journal Information:: Macromolecules, Vol. 52, Issue 9; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 14 works

Citation information provided by
Web of Science

References (55)

Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Phase Behavior of Binary Polymer Blends Doped with Salt Xie, Shuyi; Lodge, Timothy P. Macromolecules, Vol. 51, Issue 1 https://doi.org/10.1021/acs.macromol.7b02310	journal	December 2017
Phase behavior of LiClO4-doped poly(ε-caprolactone)-b-poly(ethylene oxide) hybrids in the presence of competitive interactions Huang, Jie; Tong, Zai-Zai; Zhou, Bing Polymer, Vol. 55, Issue 4 https://doi.org/10.1016/j.polymer.2014.01.012	journal	February 2014
Salt Doping in PEO-Containing Block Copolymers: Counterion and Concentration Effects Young, Wen-Shiue; Epps, Thomas H. Macromolecules, Vol. 42, Issue 7 https://doi.org/10.1021/ma802799p	journal	April 2009
Ionic Conductivity, Self-Assembly, and Viscoelasticity in Poly(styrene- b -ethylene oxide) Electrolytes Doped with LiTf Zardalidis, George; Gatsouli, Katerina; Pispas, Stergios Macromolecules, Vol. 48, Issue 19 https://doi.org/10.1021/acs.macromol.5b01596	journal	September 2015
Ion-Complexation-Induced Changes in the Interaction Parameter and the Chain Conformation of PS- b -PMMA Copolymers Wang, Jia-Yu; Chen, Wei; Russell, Thomas P. Macromolecules, Vol. 41, Issue 13 https://doi.org/10.1021/ma800718z	journal	July 2008
Phase Behavior and Ionic Conductivity of Lithium Perchlorate-Doped Polystyrene- b -poly(2-vinylpyridine) Copolymer Naidu, Sudhakar; Ahn, Hyungju; Gong, Jinsam Macromolecules, Vol. 44, Issue 15 https://doi.org/10.1021/ma200429v	journal	August 2011
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
Morphologies of block copolymers composed of charged and neutral blocks Wang, Xiaojun; Goswami, Monojoy; Kumar, Rajeev Soft Matter, Vol. 8, Issue 11 https://doi.org/10.1039/c2sm07223h	journal	January 2012
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
Effect of anion polarization on conductivity behavior of poly(ethylene oxide) complexed with alkali salts Besner, S.; Vallee, A.; Bouchard, G. Macromolecules, Vol. 25, Issue 24 https://doi.org/10.1021/ma00050a015	journal	November 1992
Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter Hu, Hanqiong; Gopinadhan, Manesh; Osuji, Chinedum O. Soft Matter, Vol. 10, Issue 22 https://doi.org/10.1039/c3sm52607k	journal	January 2014
Solvation and Entropic Regimes in Ion-Containing Block Copolymers Hou, Kevin J.; Qin, Jian Macromolecules, Vol. 51, Issue 19 https://doi.org/10.1021/acs.macromol.8b01616	journal	September 2018
The effective χ parameter in polarizable polymeric systems: One-loop perturbation theory and field-theoretic simulations Grzetic, Douglas J.; Delaney, Kris T.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 148, Issue 20 https://doi.org/10.1063/1.5025720	journal	May 2018
Multiscale Simulations of Lamellar PS–PEO Block Copolymers Doped with LiPF ₆ Ions Sethuraman, Vaidyanathan; Mogurampelly, Santosh; Ganesan, Venkat Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00125	journal	May 2017
Organic/Inorganic Hybrid Block Copolymer Electrolytes with Nanoscale Ion-Conducting Channels for Lithium Ion Batteries Kim, Sung-Kon; Kim, Dong-Gyun; Lee, Aeri Macromolecules, Vol. 45, Issue 23 https://doi.org/10.1021/ma301404q	journal	November 2012
Preparation and characterization of gel polymer electrolyte based on electrospun polyhedral oligomeric silsesquioxane-poly(methyl methacrylate)8/polyvinylidene fluoride hybrid nanofiber membranes for lithium-ion batteries Liu, Yi; Ma, Xiaoyan; Sun, Kun Journal of Solid State Electrochemistry, Vol. 22, Issue 2 https://doi.org/10.1007/s10008-017-3761-6	journal	October 2017
Solid polymer electrolyte membranes based on organic/inorganic nanocomposites with star-shaped structure for high performance lithium ion battery Zhang, Jinfang; Ma, Cheng; Liu, Jiatu Journal of Membrane Science, Vol. 509 https://doi.org/10.1016/j.memsci.2016.02.049	journal	July 2016
Solid polymer electrolytes based on crosslinkable polyoctahedral silsesquioxanes (POSS) for room temperature lithium polymer batteries Lee, Jun Young; Lee, Yong Min; Bhattacharya, Bhaskar Journal of Solid State Electrochemistry, Vol. 14, Issue 8 https://doi.org/10.1007/s10008-009-0968-1	journal	November 2009
Nanocomposite solid polymer electrolytes based on poly(ethylene oxide)/POSS-PEG (n=13.3) hybrid nanoparticles for lithium ion batteries Polu, Anji Reddy; Rhee, Hee-Woo Journal of Industrial and Engineering Chemistry, Vol. 31 https://doi.org/10.1016/j.jiec.2015.07.005	journal	November 2015
Polyhedral oligomeric silsesquioxane (POSS) reinforced-unsaturated polyester hybrid nanocomposites: Thermal, thermomechanical and morphological properties Jothibasu, S.; Chandramohan, A.; Kumar, A. Ashok Journal of Macromolecular Science, Part A, Vol. 55, Issue 5 https://doi.org/10.1080/10601325.2018.1453264	journal	March 2018
Viscoelastic Behavior of Unentangled POSS–Styrene Nanocomposites and the Modification of Macromolecular Dynamics Romo-Uribe, Angel Macromolecules, Vol. 50, Issue 18 https://doi.org/10.1021/acs.macromol.7b01645	journal	September 2017
Synthesis and Self-Assembly of a Series of n POSS- b -PEO Block Copolymers with Varying Shape Anisotropy Yu, Cheng-Bin; Ren, Li-Jun; Wang, Wei Macromolecules, Vol. 50, Issue 8 https://doi.org/10.1021/acs.macromol.7b00163	journal	April 2017
Linear Hybrid Polymer Building Blocks: Methacrylate-Functionalized Polyhedral Oligomeric Silsesquioxane Monomers and Polymers Lichtenhan, Joseph D.; Otonari, Yoshiko A.; Carr, Michael J. Macromolecules, Vol. 28, Issue 24 https://doi.org/10.1021/ma00128a067	journal	November 1995
Directed Self-Assembly of POSS Containing Block Copolymer on Lithographically Defined Chemical Template with Morphology Control by Solvent Vapor Tada, Yasuhiko; Yoshida, Hiroshi; Ishida, Yoshihito, Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma201822a	journal	December 2011
Self-Assembly and Chain-Folding in Hybrid Coil−Coil−Cube Triblock Oligomers of Polyethylene- b -Poly(ethylene oxide)- b -Polyhedral Oligomeric Silsesquioxane Miao, Jianjun; Cui, Li; Lau, Henry P. Macromolecules, Vol. 40, Issue 15 https://doi.org/10.1021/ma070770w	journal	July 2007
X-ray Characterizations of Polyethylene Polyhedral Oligomeric Silsesquioxane Copolymers Zheng, Lei; Waddon, Alan J.; Farris, Richard J. Macromolecules, Vol. 35, Issue 6 https://doi.org/10.1021/ma011855e	journal	March 2002
Highly Asymmetric Phase Behaviors of Polyhedral Oligomeric Silsesquioxane-Based Multiheaded Giant Surfactants Huang, Mingjun; Yue, Kan; Huang, Jiahao ACS Nano, Vol. 12, Issue 2 https://doi.org/10.1021/acsnano.7b08687	journal	January 2018
Experimental Formulation of Photonic Crystal Properties for Hierarchically Self-Assembled POSS–Bottlebrush Block Copolymers Chae, Chang-Geun; Yu, Yong-Guen; Seo, Ho-Bin Macromolecules, Vol. 51, Issue 9 https://doi.org/10.1021/acs.macromol.8b00298	journal	April 2018
Morphology control and inducing a curvature on the domain interface by increasing the steric bulk of polymethacrylate in POSS-containing diblock copolymers Kato, Fuminobu; Sugimoto, Shin; Chandra, Alvin Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 13 https://doi.org/10.1002/pola.28610	journal	April 2017
One-Step Direct-Patterning Template Utilizing Self-Assembly of POSS-Containing Block Copolymers Hirai, Tomoyasu; Leolukman, Melvina; Liu, Chi Chun Advanced Materials, Vol. 21, Issue 43 https://doi.org/10.1002/adma.200900518	journal	November 2009
Synthesis and Self-Assembly Behavior of Organic-Inorganic Poly(ethylene oxide)- block -Poly(MA POSS)- block -Poly( N -isopropylacrylamide) Triblock Copolymers Zheng, Yaochen; Wang, Lei; Yu, Rentong Macromolecular Chemistry and Physics, Vol. 213, Issue 4 https://doi.org/10.1002/macp.201100506	journal	February 2012
Sequential “Click” Approach to Polyhedral Oligomeric Silsesquioxane-Based Shape Amphiphiles Yue, Kan; Liu, Chang; Guo, Kai Macromolecules, Vol. 45, Issue 20 https://doi.org/10.1021/ma3013256	journal	October 2012
Concentration fluctuation of stiff polymers. I. Static structure factor Shimada, Takayuki; Doi, Masao; Okano, Koji The Journal of Chemical Physics, Vol. 88, Issue 4 https://doi.org/10.1063/1.454016	journal	February 1988
Nonlamellar Phases in Asymmetric Rod−Coil Block Copolymers at Increased Segregation Strengths Olsen, Bradley D.; Segalman, Rachel A. Macromolecules, Vol. 40, Issue 19 https://doi.org/10.1021/ma070976x	journal	September 2007
Structure and Thermodynamics of Weakly Segregated Rod−Coil Block Copolymers Olsen, Bradley D.; Segalman, Rachel A. Macromolecules, Vol. 38, Issue 24 https://doi.org/10.1021/ma051468v	journal	November 2005
Zigzag Morphology of a Poly(styrene-b-hexyl isocyanate) Rod-Coil Block Copolymer Chen, J. T.; Thomas, E. L.; Ober, C. K. Macromolecules, Vol. 28, Issue 5 https://doi.org/10.1021/ma00109a048	journal	February 1995
Analysis of the Beaucage model Hammouda, Boualem Journal of Applied Crystallography, Vol. 43, Issue 6 https://doi.org/10.1107/S0021889810033856	journal	October 2010
Effect of Stiffness on the First Cumulant and Polymer Dimensions in Solution Benmouna, M.; Akcasu, A. Ziya; Daoud, M. Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a062	journal	November 1980
Copolymers as amphiphiles in ternary mixtures: An analysis employing disorder, equimaxima, and Lifshitz lines Holyst, Robert; Schick, M. The Journal of Chemical Physics, Vol. 96, Issue 10 https://doi.org/10.1063/1.462372	journal	May 1992
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
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
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
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
Fluctuation effects in a symmetric diblock copolymer near the order–disorder transition Bates, Frank S.; Rosedale, Jeffrey H.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 92, Issue 10 https://doi.org/10.1063/1.458350	journal	May 1990
Thermodynamic interactions and correlations in mixtures of two homopolymers and a block copolymer by small angle neutron scattering Balsara, N. P.; Jonnalagadda, S. V.; Lin, C. C. The Journal of Chemical Physics, Vol. 99, Issue 12 https://doi.org/10.1063/1.465505	journal	December 1993
Responsive Solids from Cross-Linked Block Copolymers Hahn, Hyeok; Eitouni, Hany B.; Balsara, Nitash P. Physical Review Letters, Vol. 90, Issue 15 https://doi.org/10.1103/PhysRevLett.90.155505	journal	April 2003
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
Fluctuation effects in the theory of microphase separation in block copolymers Fredrickson, Glenn H.; Helfand, Eugene The Journal of Chemical Physics, Vol. 87, Issue 1 https://doi.org/10.1063/1.453566	journal	July 1987
Thermodynamic Interactions in a Model Polydiene/Polyolefin Blend Based on 1,2-Polybutadiene Qiu, Jialin; Mongcopa, Katrina I.; Han, Ruixuan Macromolecules, Vol. 51, Issue 8 https://doi.org/10.1021/acs.macromol.7b02181	journal	April 2018
A lower critical ordering transition in a diblock copolymer melt Russell, T. P.; Karis, T. E.; Gallot, Y. Nature, Vol. 368, Issue 6473 https://doi.org/10.1038/368729a0	journal	April 1994
Lower Critical Ordering Transition of Poly(ethylene oxide)- block -poly(2-vinylpyridine) Yeh, Chao-Lin; Hou, Ting; Chen, Hsin-Lung Macromolecules, Vol. 44, Issue 3 https://doi.org/10.1021/ma102322w	journal	February 2011
Lower Critical Ordering Transition of an All-Hydrocarbon Polynorbornene Diblock Copolymer Mulhearn, William D.; Register, Richard A. ACS Macro Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acsmacrolett.7b00443	journal	July 2017
Synthesis and SANS Characterization of Poly(vinyl methyl ether)- block -polystyrene Hashimoto, Takahiro; Hasegawa, Hirokazu; Hashimoto, Takeji Macromolecules, Vol. 30, Issue 22 https://doi.org/10.1021/ma9613749	journal	November 1997

Cited By (1)

Self-healing and shape-memory solid polymer electrolytes with high mechanical strength facilitated by a poly(vinyl alcohol) matrix Jo, Ye Hyang; Zhou, Binghua; Jiang, Ke Polymer Chemistry, Vol. 10, Issue 48 https://doi.org/10.1039/c9py01406c	journal	January 2019

Similar Records

Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends

Journal Article · Mon Nov 21 00:00:00 EST 2016 · Macromolecules · OSTI ID:1604684

Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi; +3 more

Composition Dependence of the Flory–Huggins Interaction Parameters of Block Copolymer Electrolytes and the Isotaksis Point

Journal Article · Thu Jul 18 00:00:00 EDT 2019 · Macromolecules · OSTI ID:1604684

Loo, Whitney S.; Sethi, Gurmukh K.; Teran, Alexander A.; +5 more

Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes

Journal Article · Tue Aug 14 00:00:00 EDT 2018 · ACS Macro Letters · OSTI ID:1604684

Sethi, Gurmukh K.; Jiang, Xi; Chakraborty, Rohan; +3 more

Related Subjects

36 MATERIALS SCIENCE
salt
scattering
electrolytes
x-ray scattering
copolymers

Title: Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

Citation Formats

References (55)

Cited By (1)

Similar Records

Related Subjects