Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization
Abstract
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 rolemore »
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
- OSTI Identifier:
- 1843009
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 17; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; salts; electrochemical cells; electrolytes; lithium; electrodes
Citation Formats
Galluzzo, Michael D., Grundy, Lorena S., Takacs, Christopher J., Cao, Chuntian, Steinrück, Hans-Georg, Fu, Sean, Rivas Valadez, Michael A., Toney, Michael F., and Balsara, Nitash P. Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization. United States: N. p., 2021.
Web. doi:10.1021/acs.macromol.1c01295.
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. Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization. United States. https://doi.org/10.1021/acs.macromol.1c01295
Galluzzo, Michael D., Grundy, Lorena S., Takacs, Christopher J., Cao, Chuntian, Steinrück, Hans-Georg, Fu, Sean, Rivas Valadez, Michael A., Toney, Michael F., and Balsara, Nitash P. Fri .
"Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization". United States. https://doi.org/10.1021/acs.macromol.1c01295. https://www.osti.gov/servlets/purl/1843009.
@article{osti_1843009,
title = {Orientation-Dependent Distortion of Lamellae in a Block Copolymer Electrolyte under DC Polarization},
author = {Galluzzo, Michael D. and Grundy, Lorena S. and Takacs, Christopher J. and Cao, Chuntian and Steinrück, Hans-Georg and Fu, Sean and Rivas Valadez, Michael A. and Toney, Michael F. and Balsara, Nitash P.},
abstractNote = {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.},
doi = {10.1021/acs.macromol.1c01295},
journal = {Macromolecules},
number = 17,
volume = 54,
place = {United States},
year = {Fri Aug 27 00:00:00 EDT 2021},
month = {Fri Aug 27 00:00:00 EDT 2021}
}
Works referenced in this record:
Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes
journal, June 2007
- Singh, Mohit; Odusanya, Omolola; Wilmes, Gregg M.
- Macromolecules, Vol. 40, Issue 13
Quantifying Lithium Salt and Polymer Density Distributions in Nanostructured Ion-Conducting Block Polymers
journal, February 2018
- Gartner, Thomas E.; Morris, Melody A.; Shelton, Cameron K.
- Macromolecules, Vol. 51, Issue 5
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research
journal, June 2020
- Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P.
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 23
Multiscale Simulations of Lamellar PS–PEO Block Copolymers Doped with LiPF 6 Ions
journal, May 2017
- Sethuraman, Vaidyanathan; Mogurampelly, Santosh; Ganesan, Venkat
- Macromolecules, Vol. 50, Issue 11
Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries
journal, October 2015
- Tu, Zhengyuan; Nath, Pooja; Lu, Yingying
- Accounts of Chemical Research, Vol. 48, Issue 11
Diffusion in Lamellae, Cylinders, and Double Gyroid Block Copolymer Nanostructures
journal, August 2018
- Shen, Kuan-Hsuan; Brown, Jonathan R.; Hall, Lisa M.
- ACS Macro Letters, Vol. 7, Issue 9
Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling
journal, December 2014
- Gilbert, Jonathan B.; Luo, Ming; Shelton, Cameron K.
- ACS Nano, Vol. 9, Issue 1
In Operando Small-Angle X-ray Scattering Investigation of Nanostructured Polymer Electrolyte for Lithium-Ion Batteries
journal, June 2018
- Möhl, Gilles E.; Metwalli, Ezzeldin; Müller-Buschbaum, Peter
- ACS Energy Letters, Vol. 3, Issue 7
Anionic polymerization: High vacuum techniques
journal, January 2000
- Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18
PyFAI, a versatile library for azimuthal regrouping
journal, March 2013
- Kieffer, Jérôme; Karkoulis, Dimitrios
- Journal of Physics: Conference Series, Vol. 425, Issue 20
Concentration and velocity profiles in a polymeric lithium-ion battery electrolyte
journal, January 2020
- Steinrück, Hans-Georg; Takacs, Christopher J.; Kim, Hong-Keun
- Energy & Environmental Science, Vol. 13, Issue 11
Discontinuous Changes in Ionic Conductivity of a Block Copolymer Electrolyte through an Order–Disorder Transition
journal, January 2012
- Teran, Alexander A.; Mullin, Scott A.; Hallinan, Daniel T.
- ACS Macro Letters, Vol. 1, Issue 2
Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte
journal, July 2014
- Chintapalli, Mahati; Chen, X. Chelsea; Thelen, Jacob L.
- Macromolecules, Vol. 47, Issue 15
Modeling of transport of small molecules in polymer blends: Application of effective medium theory
journal, February 1983
- Sax, J.; Ottino, J. M.
- Polymer Engineering and Science, Vol. 23, Issue 3
Electrochemical Thin Films at and above the Classical Limiting Current
journal, January 2005
- Chu, Kevin T.; Bazant, Martin Z.
- SIAM Journal on Applied Mathematics, Vol. 65, Issue 5
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions
journal, January 2018
- Pesko, Danielle M.; Feng, Zhange; Sawhney, Simar
- Journal of The Electrochemical Society, Vol. 165, Issue 13
Solute-volume effects in electrolyte transport
journal, July 2014
- Liu, Jing; Monroe, Charles W.
- Electrochimica Acta, Vol. 135
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator
journal, October 2010
- Hexemer, Alexander; Bras, Wim; Glossinger, James
- Journal of Physics: Conference Series, Vol. 247
Effect of salt concentration profiles on protrusion growth in lithium-polymer‑lithium cells
journal, December 2020
- Frenck, Louise; Veeraraghavan, Vijay D.; Maslyn, Jacqueline A.
- Solid State Ionics, Vol. 358
Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes
journal, July 2020
- Kim, Hong-Keun; Balsara, Nitash P.; Srinivasan, Venkat
- Journal of The Electrochemical Society, Vol. 167, Issue 11
Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes
journal, March 2009
- Gomez, Enrique D.; Panday, Ashoutosh; Feng, Edward H.
- Nano Letters, Vol. 9, Issue 3
A glimpse on all-solid-state Li-ion battery (ASSLIB) performance based on novel solid polymer electrolytes: a topical review
journal, February 2020
- Arya, Anil; Sharma, A. L.
- Journal of Materials Science, Vol. 55, Issue 15
Ionic Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations
journal, May 2012
- Young, Wen-Shiue; Epps, Thomas H.
- Macromolecules, Vol. 45, Issue 11
Recent advances in solid-state polymer electrolytes and innovative ionic liquids based polymer electrolyte systems
journal, June 2020
- Isikli, Suheda; Ryan, Kevin M.
- Current Opinion in Electrochemistry, Vol. 21
Molecular Level Differences in Ionic Solvation and Transport Behavior in Ethylene Oxide-Based Homopolymer and Block Copolymer Electrolytes
journal, February 2021
- Sharon, Daniel; Bennington, Peter; Webb, Michael A.
- Journal of the American Chemical Society, Vol. 143, Issue 8
Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013
- Yuan, Rodger; Teran, Alexander A.; Gurevitch, Inna
- Macromolecules, Vol. 46, Issue 3
Comparing Experimental Measurements of Limiting Current in Polymer Electrolytes with Theoretical Predictions
journal, January 2019
- Gribble, Daniel A.; Frenck, Louise; Shah, Deep B.
- Journal of The Electrochemical Society, Vol. 166, Issue 14
The importance of the lithium ion transference number in lithium/polymer cells
journal, September 1994
- Doyle, Marc; Fuller, Thomas F.; Newman, John
- Electrochimica Acta, Vol. 39, Issue 13
Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends
journal, September 2016
- Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi
- Macromolecules, Vol. 49, Issue 18
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review
journal, July 2017
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Chemical Reviews, Vol. 117, Issue 15
Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes
journal, January 2017
- Pesko, Danielle M.; Timachova, Ksenia; Bhattacharya, Rajashree
- Journal of The Electrochemical Society, Vol. 164, Issue 11
Relationship between Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Conductivity in Polymer Electrolytes
journal, March 2018
- Mongcopa, Katrina Irene S.; Tyagi, Madhusudan; Mailoa, Jonathan P.
- ACS Macro Letters, Vol. 7, Issue 4
Unveiling the Ion Conduction Mechanism in Imidazolium-Based Poly(ionic liquids): A Comprehensive Investigation of the Structure-to-Transport Interplay
journal, May 2017
- Delhorbe, Virginie; Bresser, Dominic; Mendil-Jakani, Hakima
- Macromolecules, Vol. 50, Issue 11
Current-Induced Formation of Gradient Crystals in Block Copolymer Electrolytes
journal, December 2011
- Mullin, Scott A.; Stone, Gregory M.; Teran, Alexander A.
- Nano Letters, Vol. 12, Issue 1
Ordering Kinetics and Alignment of Block Copolymer Lamellae under Shear Flow
journal, May 1999
- Wang, H.; Newstein, M. C.; Krishnan, A.
- Macromolecules, Vol. 32, Issue 11
Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies
journal, January 2020
- Galluzzo, Michael D.; Loo, Whitney S.; Wang, Andrew A.
- The Journal of Physical Chemistry B, Vol. 124, Issue 5
Negative Stefan-Maxwell Diffusion Coefficients and Complete Electrochemical Transport Characterization of Homopolymer and Block Copolymer Electrolytes
journal, January 2018
- Villaluenga, Irune; Pesko, Danielle M.; Timachova, Ksenia
- Journal of The Electrochemical Society, Vol. 165, Issue 11
Potentiometric MRI of a Superconcentrated Lithium Electrolyte: Testing the Irreversible Thermodynamics Approach
journal, August 2021
- Wang, Andrew A.; Gunnarsdóttir, Anna B.; Fawdon, Jack
- ACS Energy Letters, Vol. 6, Issue 9
Dynamic Structure and Phase Behavior of a Block Copolymer Electrolyte under dc Polarization
journal, December 2020
- Galluzzo, Michael D.; Loo, Whitney S.; Schaible, Eric
- ACS Applied Materials & Interfaces, Vol. 12, Issue 51
Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes
journal, July 2019
- Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B.
- The Journal of Chemical Physics, Vol. 151, Issue 2
Electrochemical characterisation and modelling of the mass transport phenomena in LiPF6–EC–EMC electrolyte
journal, September 2008
- Nyman, Andreas; Behm, Mårten; Lindbergh, Göran
- Electrochimica Acta, Vol. 53, Issue 22
Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit
journal, February 2016
- Chintapalli, Mahati; Le, Thao N. P.; Venkatesan, Naveen R.
- Macromolecules, Vol. 49, Issue 5
A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids
journal, May 2021
- Zhang, Zidan; Krajniak, Jakub; Ganesan, Venkat
- Macromolecules, Vol. 54, Issue 11
Thermodynamics of Block Copolymers with and without Salt
journal, December 2013
- Teran, Alexander A.; Balsara, Nitash P.
- The Journal of Physical Chemistry B, Vol. 118, Issue 1
Role of Defects in Ion Transport in Block Copolymer Electrolytes
journal, June 2019
- Kambe, Yu; Arges, Christopher G.; Czaplewski, David A.
- Nano Letters, Vol. 19, Issue 7
Limiting Current in Nanostructured Block Copolymer Electrolytes
journal, April 2021
- Maslyn, Jacqueline A.; Frenck, Louise; Veeraraghavan, Vijay D.
- Macromolecules, Vol. 54, Issue 9