Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization

Galluzzo, Michael D.; Grundy, Lorena S.; Takacs, Christopher J.; Cao, Chuntian; Steinrück, Hans-Georg; Fu, Sean; Rivas Valadez, Michael A.; Toney, Michael F.; Balsara, Nitash P.

doi:10.1021/acs.macromol.1c01295

Title: Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization

Journal Article · Fri Aug 27 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c01295· OSTI ID:1843009

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^[1]; Takacs, Christopher J. ^[2];

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^[4]; Fu, Sean ^[5]; Rivas Valadez, Michael A. ^[5];

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Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Colorado, Boulder, CO (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. Paderborn (Germany)
Univ. of California, Berkeley, CA (United States)
Univ. of Colorado, Boulder, CO (United States)

Lithium-salt-doped block copolymers have the potential to serve as solid electrolytes in rechargeable batteries with lithium metal anodes. In this work, we use small-angle X-ray scattering (SAXS) to study the structure of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) doped with bis-(trifluoromethylsulfonyl)amine lithium salt (LiTFSI) during direct current (dc) polarization experiments in lithiu-lithium symmetric cells. The block copolymer studied is nearly symmetric in composition, has a total molecular weight of 39 kg mol^-1, and exhibits a lamellar morphology at all studied salt concentrations. When ionic current is passed through the electrolyte, a salt concentration gradient forms that induces a spatial gradient in the domain spacing, d. The dependence of d on distance from the positive electrode, x, was determined experimentally by scanning the incident X-ray beam from one lithium electrode to the other. By studying the two-dimensional (2D) SAXS patterns as a function of azimuthal scattering angle, we find that lamellae with PS/PEO interfaces oriented perpendicular to the flow of ionic current (LAM_⟂) swell and contract to a greater degree than those with interfaces oriented parallel to the current direction (LAM_||). While domains with the LAM_⟂ do not provide direct conducting pathways between the electrodes, our analysis suggests that they play an important role in establishing the salt concentration gradient necessary for sustaining a large ionic current through greater expansion and contraction.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC02-06CH11357

OSTI ID:: 1843009

Journal Information:: Macromolecules, Vol. 54, Issue 17; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

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
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
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P. Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821672117	journal	June 2020
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
Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries Tu, Zhengyuan; Nath, Pooja; Lu, Yingying Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00427	journal	October 2015
Diffusion in Lamellae, Cylinders, and Double Gyroid Block Copolymer Nanostructures Shen, Kuan-Hsuan; Brown, Jonathan R.; Hall, Lisa M. ACS Macro Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsmacrolett.8b00506	journal	August 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
In Operando Small-Angle X-ray Scattering Investigation of Nanostructured Polymer Electrolyte for Lithium-Ion Batteries Möhl, Gilles E.; Metwalli, Ezzeldin; Müller-Buschbaum, Peter ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00763	journal	June 2018
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
PyFAI, a versatile library for azimuthal regrouping Kieffer, Jérôme; Karkoulis, Dimitrios Journal of Physics: Conference Series, Vol. 425, Issue 20 https://doi.org/10.1088/1742-6596/425/20/202012	journal	March 2013
Concentration and velocity profiles in a polymeric lithium-ion battery electrolyte Steinrück, Hans-Georg; Takacs, Christopher J.; Kim, Hong-Keun Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE02193H	journal	January 2020
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
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
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
Electrochemical Thin Films at and above the Classical Limiting Current Chu, Kevin T.; Bazant, Martin Z. SIAM Journal on Applied Mathematics, Vol. 65, Issue 5 https://doi.org/10.1137/040609926	journal	January 2005
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions Pesko, Danielle M.; Feng, Zhange; Sawhney, Simar Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0921813jes	journal	January 2018
Solute-volume effects in electrolyte transport Liu, Jing; Monroe, Charles W. Electrochimica Acta, Vol. 135 https://doi.org/10.1016/j.electacta.2014.05.009	journal	July 2014
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
Effect of salt concentration profiles on protrusion growth in lithium-polymer‑lithium cells Frenck, Louise; Veeraraghavan, Vijay D.; Maslyn, Jacqueline A. Solid State Ionics, Vol. 358 https://doi.org/10.1016/j.ssi.2020.115517	journal	December 2020
Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes Kim, Hong-Keun; Balsara, Nitash P.; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/aba790	journal	July 2020
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
A glimpse on all-solid-state Li-ion battery (ASSLIB) performance based on novel solid polymer electrolytes: a topical review Arya, Anil; Sharma, A. L. Journal of Materials Science, Vol. 55, Issue 15 https://doi.org/10.1007/s10853-020-04434-8	journal	February 2020
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
Recent advances in solid-state polymer electrolytes and innovative ionic liquids based polymer electrolyte systems Isikli, Suheda; Ryan, Kevin M. Current Opinion in Electrochemistry, Vol. 21 https://doi.org/10.1016/j.coelec.2020.01.015	journal	June 2020
Molecular Level Differences in Ionic Solvation and Transport Behavior in Ethylene Oxide-Based Homopolymer and Block Copolymer Electrolytes Sharon, Daniel; Bennington, Peter; Webb, Michael A. Journal of the American Chemical Society, Vol. 143, Issue 8 https://doi.org/10.1021/jacs.0c12538	journal	February 2021
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
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions Gribble, Daniel A.; Frenck, Louise; Shah, Deep B. Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.0391914jes	journal	January 2019
The importance of the lithium ion transference number in lithium/polymer cells Doyle, Marc; Fuller, Thomas F.; Newman, John Electrochimica Acta, Vol. 39, Issue 13 https://doi.org/10.1016/0013-4686(94)85091-7	journal	September 1994
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
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
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
Relationship between Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Conductivity in Polymer Electrolytes Mongcopa, Katrina Irene S.; Tyagi, Madhusudan; Mailoa, Jonathan P. ACS Macro Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acsmacrolett.8b00159	journal	March 2018
Unveiling the Ion Conduction Mechanism in Imidazolium-Based Poly(ionic liquids): A Comprehensive Investigation of the Structure-to-Transport Interplay Delhorbe, Virginie; Bresser, Dominic; Mendil-Jakani, Hakima Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00197	journal	May 2017
Current-Induced Formation of Gradient Crystals in Block Copolymer Electrolytes Mullin, Scott A.; Stone, Gregory M.; Teran, Alexander A. Nano Letters, Vol. 12, Issue 1 https://doi.org/10.1021/nl203826s	journal	December 2011
Ordering Kinetics and Alignment of Block Copolymer Lamellae under Shear Flow Wang, H.; Newstein, M. C.; Krishnan, A. Macromolecules, Vol. 32, Issue 11 https://doi.org/10.1021/ma981226d	journal	May 1999
Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies Galluzzo, Michael D.; Loo, Whitney S.; Wang, Andrew A. The Journal of Physical Chemistry B, Vol. 124, Issue 5 https://doi.org/10.1021/acs.jpcb.9b11066	journal	January 2020
Negative Stefan-Maxwell Diffusion Coefficients and Complete Electrochemical Transport Characterization of Homopolymer and Block Copolymer Electrolytes Villaluenga, Irune; Pesko, Danielle M.; Timachova, Ksenia Journal of The Electrochemical Society, Vol. 165, Issue 11 https://doi.org/10.1149/2.0641811jes	journal	January 2018
Potentiometric MRI of a Superconcentrated Lithium Electrolyte: Testing the Irreversible Thermodynamics Approach Wang, Andrew A.; Gunnarsdóttir, Anna B.; Fawdon, Jack ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01213	journal	August 2021
Dynamic Structure and Phase Behavior of a Block Copolymer Electrolyte under dc Polarization Galluzzo, Michael D.; Loo, Whitney S.; Schaible, Eric ACS Applied Materials & Interfaces, Vol. 12, Issue 51 https://doi.org/10.1021/acsami.0c16209	journal	December 2020
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
Electrochemical characterisation and modelling of the mass transport phenomena in LiPF6–EC–EMC electrolyte Nyman, Andreas; Behm, Mårten; Lindbergh, Göran Electrochimica Acta, Vol. 53, Issue 22 https://doi.org/10.1016/j.electacta.2008.04.023	journal	September 2008
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
A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids Zhang, Zidan; Krajniak, Jakub; Ganesan, Venkat Macromolecules, Vol. 54, Issue 11 https://doi.org/10.1021/acs.macromol.1c00025	journal	May 2021
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
Role of Defects in Ion Transport in Block Copolymer Electrolytes Kambe, Yu; Arges, Christopher G.; Czaplewski, David A. Nano Letters, Vol. 19, Issue 7 https://doi.org/10.1021/acs.nanolett.9b01758	journal	June 2019
Limiting Current in Nanostructured Block Copolymer Electrolytes Maslyn, Jacqueline A.; Frenck, Louise; Veeraraghavan, Vijay D. Macromolecules, Vol. 54, Issue 9 https://doi.org/10.1021/acs.macromol.1c00425	journal	April 2021

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Title: Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization

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