Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes

Yang, Guang; Cao, Peng-Fei; Self, Ethan C.; Lehmann, Michelle; Chen, Xi Chelsea; Zhao, Sheng; Ge, Sirui; Zhu, Chenhui; Saito, Tomonori; Delnick, Frank M.; Nanda, Jagjit

doi:10.1149/1945-7111/ac6a18

Title: Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes

Journal Article · Wed May 04 00:00:00 EDT 2022 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac6a18· OSTI ID:1892417

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

The plasticization of a polymer electrolyte usually promotes its ionic conductivity but decreases its storage modulus due to the increased polymer chain flexibility. Herein, we show that such a tradeoff between the ionic conductivity and the mechanical robustness of the polymer electrolyte can be alleviated by selective plasticization of the ion-conductive block, such as poly(ethylene oxide) (PEO) in a polystyrene (PS)– PEO–PS block copolymer (SEO) electrolyte using an ether type plasticizer, tetraethylene glycol dimethyl ether (TEGDME). In this work, at maximum plasticizer loading, the room temperature ionic conductivity increases by up to 3 orders, whereas the storage modulus, G' reduces to half, is still on the order of 10² MPa. At above the melting temperature of the PEO block, the dynamic storage modulus, G' of the plasticized membrane surpasses its dry PS-PEO-PS counterpart. Such a phenomenon results from that, a) TEGDME co-crystallizes with PEO to promote its crystallinity and hence the storage modulus, b) TEGDME swells the amorphous PEO phase to enhance the polymer chain segmental mobility and hence ionic conductivity, and c) the PS phase remains intact from TEGDME to keep the SEO elastic.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

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

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1892417

Journal Information:: Journal of the Electrochemical Society, Vol. 169, Issue 5; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (31)

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
Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study Gunkel, Ilja; Thurn-Albrecht, Thomas Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma201334h	journal	December 2011
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
High Toughness, High Conductivity Ion Gels by Sequential Triblock Copolymer Self-Assembly and Chemical Cross-Linking Gu, Yuanyan; Zhang, Sipei; Martinetti, Luca Journal of the American Chemical Society, Vol. 135, Issue 26 https://doi.org/10.1021/ja4051394	journal	June 2013
Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries Inceoglu, Sebnem; Rojas, Adriana A.; Devaux, Didier ACS Macro Letters, Vol. 3, Issue 6 https://doi.org/10.1021/mz5001948	journal	May 2014
Charge Carrier Relaxation in Different Plasticized PEO/PVDF-HFP Blend Solid Polymer Electrolytes Das, S.; Ghosh, A. The Journal of Physical Chemistry B, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcb.7b02277	journal	May 2017
Crystal Growth Rate in a Blend of Long and Short Polymer Chains Carvalho, Jessica L.; Cormier, Sara L.; Lin, Nan Macromolecules, Vol. 45, Issue 3 https://doi.org/10.1021/ma202429q	journal	January 2012
Anomalously high elastic modulus of a poly(ethylene oxide)-based composite electrolyte Yang, Guang; Lehmann, Michelle L.; Zhao, Sheng Energy Storage Materials, Vol. 35 https://doi.org/10.1016/j.ensm.2020.11.031	journal	March 2021
Review on gel polymer electrolytes for lithium batteries Manuel Stephan, A. European Polymer Journal, Vol. 42, Issue 1 https://doi.org/10.1016/j.eurpolymj.2005.09.017	journal	January 2006
Mechanically Robust, Sodium-Ion Conducting Membranes for Nonaqueous Redox Flow Batteries Ruther, Rose E.; Yang, Guang; Delnick, Frank M. ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00680	journal	June 2018
Phase Behavior and Morphology of Poly(ethylene oxide) Blends Balijepalli, S.; Schultz, J. M.; Lin, J. S. Macromolecules, Vol. 29, Issue 20 https://doi.org/10.1021/ma960678s	journal	January 1996
Molecular Dynamics Simulations and Vibrational Spectroscopic Studies of Local Structure in Tetraglyme:Sodium Triflate (CH ₃ O(CH ₂ CH ₂ O) ₄ CH ₃ :NaCF ₃ SO ₃ ) Solutions Dong, Haitao; Hyun, Jin-Kee; Rhodes, Christopher P. The Journal of Physical Chemistry B, Vol. 106, Issue 18 https://doi.org/10.1021/jp013914w	journal	May 2002
Nanocomposite polymer electrolytes for lithium batteries Croce, F.; Appetecchi, G. B.; Persi, L. Nature, Vol. 394, Issue 6692 https://doi.org/10.1038/28818	journal	July 1998
Ionic conductivity of plasticized(PEO)-LiCF3SO3 electrolytes Bandara, L. R. A. K.; Dissanayake, M. A. K. L.; Mellander, B. -E. Electrochimica Acta, Vol. 43, Issue 10-11 https://doi.org/10.1016/S0013-4686(97)10082-2	journal	April 1998
The design space for long-duration energy storage in decarbonized power systems Sepulveda, Nestor A.; Jenkins, Jesse D.; Edington, Aurora Nature Energy, Vol. 6, Issue 5 https://doi.org/10.1038/s41560-021-00796-8	journal	March 2021
Structure-directed self-assembly of alkyl-aryl-ethylene oxide amphiphiles Liu, Gao; Baker, Gregory L. Soft Matter, Vol. 4, Issue 5 https://doi.org/10.1039/b716041k	journal	January 2008
Elastic Single-Ion Conducting Polymer Electrolytes: Toward a Versatile Approach for Intrinsically Stretchable Functional Polymers Cao, Peng-Fei; Li, Bingrui; Yang, Guang Macromolecules, Vol. 53, Issue 9 https://doi.org/10.1021/acs.macromol.9b02683	journal	April 2020
Electrical conductivity of poly(ethylene oxide)—alkali metal salt systems and effects of mixed salts and mixed molecular weights Preechatiwong, Wanchart; Schultz, Jerold M. Polymer, Vol. 37, Issue 23 https://doi.org/10.1016/0032-3861(96)00332-1	journal	November 1996
Effect of LiClO ₄ on the Structure and Mobility of PEO-Based Solid Polymer Electrolytes Fullerton-Shirey, Susan K.; Maranas, Janna K. Macromolecules, Vol. 42, Issue 6 https://doi.org/10.1021/ma802502u	journal	March 2009
Melt-Formable Block Copolymer Electrolytes for Lithium Rechargeable Batteries Ruzette, Anne-Valérie G.; Soo, Philip P.; Sadoway, Donald R. Journal of The Electrochemical Society, Vol. 148, Issue 6 https://doi.org/10.1149/1.1368097	journal	January 2001
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
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
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
Crystallinity and Chain Conformation in PEO/Layered Silicate Nanocomposites Chrissopoulou, K.; Andrikopoulos, K. S.; Fotiadou, S. Macromolecules, Vol. 44, Issue 24 https://doi.org/10.1021/ma201711r	journal	December 2011
Effect of Salt Concentration on the Conductivity of PEO-Based Composite Polymeric Electrolytes Wieczorek, Władysław; Raducha, Dorota; Zalewska, Aldona The Journal of Physical Chemistry B, Vol. 102, Issue 44 https://doi.org/10.1021/jp982403f	journal	October 1998
A star-shaped single lithium-ion conducting copolymer by grafting a POSS nanoparticle Cao, Peng-Fei; Wojnarowska, Zaneta; Hong, Tao Polymer, Vol. 124 https://doi.org/10.1016/j.polymer.2017.07.052	journal	August 2017
Rational Polymer Design of Stretchable Poly(ionic liquid) Membranes for Dual Applications Li, Bingrui; Zhao, Sheng; Zhu, Jiadeng Macromolecules, Vol. 54, Issue 2 https://doi.org/10.1021/acs.macromol.0c02335	journal	December 2020
Tailored crosslinking of Poly(ethylene oxide) enables mechanical robustness and improved sodium-ion conductivity Lehmann, Michelle L.; Yang, Guang; Gilmer, Dustin Energy Storage Materials, Vol. 21 https://doi.org/10.1016/j.ensm.2019.06.028	journal	September 2019
Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua Journal of Power Sources, Vol. 390 https://doi.org/10.1016/j.jpowsour.2018.04.006	journal	June 2018
Structural Dynamics of Strongly Segregated Block Copolymer Electrolytes Oparaji, Onyekachi; Narayanan, Suresh; Sandy, Alec Macromolecules, Vol. 51, Issue 7 https://doi.org/10.1021/acs.macromol.7b01803	journal	March 2018
Long-Duration Electricity Storage Applications, Economics, and Technologies Albertus, Paul; Manser, Joseph S.; Litzelman, Scott Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.11.009	journal	January 2020

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