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

Thelen, Jacob L.; Wang, Andrew A.; Chen, X. Chelsea; Jiang, Xi; Schaible, Eric; Balsara, Nitash P.

doi:10.1021/acs.macromol.7b02415

Title: 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

DOI:https://doi.org/10.1021/acs.macromol.7b02415· OSTI ID:1465706

^[1]; Wang, Andrew A. ^[2];

^[3]; Jiang, Xi ^[3]; Schaible, Eric ^[4];

^[5]

Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division and Joint Center for Energy Storage Research (JCESR)
Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division, Joint Center for Energy Storage Research (JCESR) and Environmental Energy Technologies Division

Block copolymer electrolytes have been shown to increase the cycle life of rechargeable batteries that utilize high capacity lithium anodes. Most block copolymer electrolyte studies have been centered on polystyrene-b-poly(ethylene oxide) (SEO) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and are limited to salt concentrations in the vicinity of r[Li]/[EO] = 0.1, where [Li] and [EO] are the concentration of lithium and ethylene oxide moieties, respectively, as the conductivity of poly(ethylene oxide) (PEO) homopolymer electrolytes is maximized at this concentration.Here, in this paper, we study the morphology and conductivity of electrolytes derived from a high molecular weight SEO block copolymer over the wide LiTFSI concentration range of 0 ≤ r ≤ 0.550. For electrolytes with r ≥ 0.125, the crystallization of PEO-LiTFSI complexes with stoichiometric ratios of 6:1, 3:1, or 2:1 (EO:Li) is shown to correlate with morphology as determined by small-angle X-ray scattering (SAXS) and scanning transmission electron microscopy (STEM): some samples that are semicrystalline at room temperature exhibit regions of periodic lamellar ordering, whereas those that do not crystallize have aperiodic packed-ellipsoid morphologies. SAXS profiles below and above the melting temperatures of the crystals are identical, indicating that the crystals are confined within the block copolymer domains. The conductivities of SEO/LiTFSI mixtures with r = 0.275, r = 0.300, and r = 0.350 are within experimental error of PEO/LiTFSI at the same salt concentrations, in spite of the presence of insulating polystyrene (PS) domains in the SEO/LiTFSI samples. We attribute this to enhanced segmental dynamics of the PEO chains in the SEO electrolytes, based on differential scanning calorimetry (DSC) measurements of glass transition temperatures. The dependence of ionic conductivity on salt concentration in the SEO/LiTFSI electrolytes at temperatures above the melting temperature of the crystalline complexes shows three local maxima that correlate with the formation of crystalline complexes when r ≥ 0.125. Finally, these maxima arise due to a combination of the enhanced segmental dynamics and changes in morphology observed by SAXS and STEM.

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

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

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

OSTI ID:: 1465706

Journal Information:: Macromolecules, Vol. 51, Issue 5; Related Information: © 2018 American Chemical Society.; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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References (40)

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
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 152, Issue 2 https://doi.org/10.1149/1.1850854	journal	January 2005
Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode Harry, Katherine J.; Higa, Kenneth; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0191610jes	journal	January 2016
Lithium Metal Stability in Batteries with Block Copolymer Electrolytes Hallinan, Daniel T.; Mullin, Scott A.; Stone, Gregory M. Journal of The Electrochemical Society, Vol. 160, Issue 3 https://doi.org/10.1149/2.030303jes	journal	January 2013
Lithium Dendrite Growth in Glassy and Rubbery Nanostructured Block Copolymer Electrolytes Schauser, Nicole S.; Harry, Katherine J.; Parkinson, Dilworth Y. Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0511503jes	journal	December 2014
Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries Khurana, Rachna; Schaefer, Jennifer L.; Archer, Lynden A. Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja502133j	journal	May 2014
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
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 Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations Young, Wen-Shiue; Epps, Thomas H. Macromolecules, Vol. 45, Issue 11 https://doi.org/10.1021/ma300362f	journal	May 2012
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
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D. Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma900451e	journal	July 2009
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
Optimization of Block Copolymer Electrolytes for Lithium Metal Batteries Devaux, Didier; Glé, David; Phan, Trang N. T. Chemistry of Materials, Vol. 27, Issue 13 https://doi.org/10.1021/acs.chemmater.5b01273	journal	June 2015
ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties Bates, Christopher M.; Chang, Alice B.; Momčilović, Nebojša Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/acs.macromol.5b00880	journal	July 2015
Phase behavior and Li ⁺ Ion conductivity of styrene‐ethylene oxide multiblock copolymer electrolytes Sarapas, Joel M.; Saijo, Kenji; Zhao, Yue Polymers for Advanced Technologies, Vol. 27, Issue 7 https://doi.org/10.1002/pat.3753	journal	February 2016
Modulating Ion Transport and Self-Assembly of Polymer Electrolytes via End-Group Chemistry Jung, Ha Young; Mandal, Prithwiraj; Jo, Gyuha Macromolecules, Vol. 50, Issue 8 https://doi.org/10.1021/acs.macromol.7b00249	journal	April 2017
Simple Route for Tuning the Morphology and Conductivity of Polymer Electrolytes: One End Functional Group is Enough Jo, Gyuha; Ahn, Hyungmin; Park, Moon Jeong ACS Macro Letters, Vol. 2, Issue 11 https://doi.org/10.1021/mz400468m	journal	October 2013
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
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
Lithium-Salt-Containing High-Molecular-Weight Polystyrene- block -Polyethylene Oxide Block Copolymer Films Metwalli, Ezzeldin; Rasool, Majid; Brunner, Simon ChemPhysChem, Vol. 16, Issue 13 https://doi.org/10.1002/cphc.201500358	journal	August 2015
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
Butyllithium-Initiated Anionic Synthesis of Well-Defined Poly(styrene-block-ethylene oxide) Block Copolymers with Potassium Salt Additives Quirk, Roderic P.; Kim, Jungahn; Kausch, Charles Polymer International, Vol. 39, Issue 1, p. 3-10 https://doi.org/10.1002/(SICI)1097-0126(199601)39:1<3::AID-PI436>3.0.CO;2-O	journal	January 1996
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
Physical Properties of Polymers Handbook Mark, James E. https://doi.org/10.1007/978-0-387-69002-5	book	January 2007
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
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
Influence of Miscibility on Poly(ethylene oxide) Crystallization from Disordered Melts of Block Copolymers with Lithium and Magnesium Counterions Thelen, Jacob L.; Chen, X. Chelsea; Inceoglu, Sebnem Macromolecules, Vol. 50, Issue 12 https://doi.org/10.1021/acs.macromol.7b00735	journal	June 2017
Glassy Carbon as an Absolute Intensity Calibration Standard for Small-Angle Scattering Zhang, Fan; Ilavsky, Jan; Long, Gabrielle G. Metallurgical and Materials Transactions A, Vol. 41, Issue 5 https://doi.org/10.1007/s11661-009-9950-x	journal	August 2009
Crystalline phases, morphology and conductivity of PEO:LiTFSI electrolytes in the eutectic region Marzantowicz, M.; Dygas, J. R.; Krok, F. Journal of Power Sources, Vol. 159, Issue 1 https://doi.org/10.1016/j.jpowsour.2006.02.044	journal	September 2006
Influence of crystalline complexes on electrical properties of PEO:LiTFSI electrolyte Marzantowicz, M.; Dygas, J. R.; Krok, F. Electrochimica Acta, Vol. 53, Issue 4 https://doi.org/10.1016/j.electacta.2007.03.032	journal	December 2007
Influence of crystallization on dielectric properties of PEO:LiTFSI polymer electrolyte Marzantowicz, M.; Dygas, J. R.; Krok, F. Journal of Non-Crystalline Solids, Vol. 352, Issue 42-49 https://doi.org/10.1016/j.jnoncrysol.2006.02.161	journal	November 2006
Structure of the polymer electrolyte poly(ethylene oxide)3: LiN(SO2CF3)2 determined by powder diffraction using a powerful Monte Carlo approach Andreev, Y. G.; Lightfoot, P.; Bruce, P. G. Chemical Communications, Issue 18 https://doi.org/10.1039/cc9960002169	journal	January 1996
Using crystallography to understand polymer electrolytes Andreev, Yuri G.; Bruce, Peter G. Journal of Physics: Condensed Matter, Vol. 13, Issue 36 https://doi.org/10.1088/0953-8984/13/36/302	journal	August 2001
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
Crystallization Temperature-Dependent Crystal Orientations within Nanoscale Confined Lamellae of a Self-Assembled Crystalline−Amorphous Diblock Copolymer Zhu, Lei; Cheng, Stephen Z. D.; Calhoun, Bret H. Journal of the American Chemical Society, Vol. 122, Issue 25 https://doi.org/10.1021/ja000275e	journal	June 2000
Relaxation in polymer electrolytes on the nanosecond timescale Mao, Guomin; Perea, Ricardo Fernandez; Howells, W. Spencer Nature, Vol. 405, Issue 6783 https://doi.org/10.1038/35012032	journal	May 2000
α-Relaxation in PEO−LiTFSI Polymer Electrolytes Mao, Guomin; Saboungi, Marie-Louise; Price, David L. Macromolecules, Vol. 35, Issue 2 https://doi.org/10.1021/ma010108e	journal	January 2002
Solvation effect upon glass transition temperature and conductivity of poly(ethylene oxide) complexed with alkali thiocyanates Besner, S.; Prud'homme, J. Macromolecules, Vol. 22, Issue 7 https://doi.org/10.1021/ma00197a026	journal	July 1989
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
Modeling of transport of small molecules in polymer blends: Application of effective medium theory Sax, J.; Ottino, J. M. Polymer Engineering and Science, Vol. 23, Issue 3 https://doi.org/10.1002/pen.760230310	journal	February 1983

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