Anomalously high elastic modulus of a poly(ethylene oxide)-based composite electrolyte

Yang, Guang; Lehmann, Michelle L.; Zhao, Sheng; Li, Bingrui; Ge, Sirui; Cao, Peng-Fei; Delnick, Frank M.; Sokolov, Alexei P.; Saito, Tomonori; Nanda, Jagjit

doi:10.1016/j.ensm.2020.11.031

Title: Anomalously high elastic modulus of a poly(ethylene oxide)-based composite electrolyte

Journal Article · Fri Nov 20 00:00:00 EST 2020 · Energy Storage Materials

DOI:https://doi.org/10.1016/j.ensm.2020.11.031· OSTI ID:1755308

^[1]; Lehmann, Michelle L. ^[2]; Zhao, Sheng ^[3];

^[3]; Ge, Sirui ^[3];

^[1];

^[2];

^[2]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)

The practical use of lithium metal anodes in solid-state batteries requires a polymer membrane with high lithium-ion conductivity, thermal/electrochemical stability, and mechanical strength. The primary challenge is to effectively decouple the ionic conductivity and mechanical strength of the polymer electrolytes. We report a remarkably facile single step synthetic strategy based on in-situ crosslinking of poly(ethylene oxide) (xPEO) in the presence of a woven glass fiber (GF). Such a simple method yields composite polymer electrolytes (CPE) of anomalously high elastic modulus up to 2.5 GPa over a broad temperature range (20 °C – 245 °C) that has never been previously documented. An unsupervised machine learning algorithm, K-mean clustering analysis, was implemented on the hyperspectral Raman mapping at the xPEO/GF interface. Using such a unique means, we show for the first time that the promoted mechanical strength originates from xPEO and GF interactions through dynamic hydrogen and ionic bonding. High ionic conductivity is achieved by the addition plasticizer (e.g. tetraglyme), where trifluoromethanesulfonate anions are tethered to the xPEO matrix and Li⁺ cations are favorably transported through coordination with the plasticizer. Further, stringent galvanostatic cycling tests indicates the CPE can be stably cycled for >3000 h in a Li-metal symmetric cell at a moderate temperature (nearly 1500 Coulombs/cm² Li equivalents), outperforming most of the PEO-based electrolytes. The GF reinforced CPE reported here has multifunctional uses, such as solid electrolytes for all solid-state batteries and membranes for redox-flow batteries. Although the focus of this study is on lithium-based batteries, the results are equally promising for other alkali metal based batteries such as sodium and potassium.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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; USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1755308

Alternate ID(s):: OSTI ID: 1809845

Journal Information:: Energy Storage Materials, Vol. 35, Issue 35; ISSN 2405-8297

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid Liu, Jun; Zhang, Ji-Guang; Yang, Zhenguo Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200690	journal	June 2012
Progress and prospects of next-generation redox flow batteries Zhang, Changkun; Zhang, Leyuan; Ding, Yu Energy Storage Materials, Vol. 15 https://doi.org/10.1016/j.ensm.2018.06.008	journal	November 2018
Recent advances of electrode materials for low-cost sodium-ion batteries towards practical application for grid energy storage Li, Yunming; Lu, Yaxiang; Zhao, Chenglong Energy Storage Materials, Vol. 7 https://doi.org/10.1016/j.ensm.2017.01.002	journal	April 2017
A silicon anode for garnet-based all-solid-state batteries: Interfaces and nanomechanics Ping, Weiwei; Yang, Chunpeng; Bao, Yinhua Energy Storage Materials, Vol. 21 https://doi.org/10.1016/j.ensm.2019.06.024	journal	September 2019
Exploring Bio-inspired Quinone-Based Organic Redox Flow Batteries: A Combined Experimental and Computational Study Ding, Yu; Li, Yafei; Yu, Guihua Chem, Vol. 1, Issue 5 https://doi.org/10.1016/j.chempr.2016.09.004	journal	November 2016
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
Origin of lithium whisker formation and growth under stress He, Yang; Ren, Xiaodi; Xu, Yaobin Nature Nanotechnology, Vol. 14, Issue 11 https://doi.org/10.1038/s41565-019-0558-z	journal	October 2019
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
Chemically inert covalently networked triazole-based solid polymer electrolytes for stable all-solid-state lithium batteries Shi, Yi; Chen, Yang; Liang, Yanliang Journal of Materials Chemistry A, Vol. 7, Issue 34 https://doi.org/10.1039/C9TA05885K	journal	January 2019
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
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
Crystallization Kinetics of Glyme−LiX and PEO−LiX Polymer Electrolytes Henderson, Wesley A. Macromolecules, Vol. 40, Issue 14 https://doi.org/10.1021/ma061866d	journal	July 2007
Well-designed Crosslinked Polymer Electrolyte Enables High Ionic Conductivity and Enhanced Salt Solvation Lehmann, Michelle L.; Yang, Guang; Nanda, Jagjit Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab7c6e	journal	January 2020
Hyperbranched PEO-Based Hyperstar Solid Polymer Electrolytes with Simultaneous Improvement of Ion Transport and Mechanical Strength Chen, Yang; Shi, Yi; Liang, Yanliang ACS Applied Energy Materials, Vol. 2, Issue 3 https://doi.org/10.1021/acsaem.8b02188	journal	February 2019
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
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
High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO ₂ Nanospheres in Poly(ethylene oxide) Lin, Dingchang; Liu, Wei; Liu, Yayuan Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04117	journal	December 2015
Nanocomposites of Titanium Dioxide and Polystyrene-Poly(ethylene oxide) Block Copolymer as Solid-State Electrolytes for Lithium Metal Batteries Gurevitch, Inna; Buonsanti, Raffaella; Teran, Alexander A. Journal of The Electrochemical Society, Vol. 160, Issue 9 https://doi.org/10.1149/2.117309jes	journal	January 2013
Free-Standing PEO/LiTFSI/LAGP Composite Electrolyte Membranes for Applications to Flexible Solid-State Lithium-Based Batteries Lee, Jeremy; Howell, Thomas; Rottmayer, Michael Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.1321902jes	journal	January 2019
Crosslinkable fumed silica-based nanocomposite electrolytes for rechargeable lithium batteries Li, Yangxing; Yerian, Jeffrey A.; Khan, Saad A. Journal of Power Sources, Vol. 161, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.06.015	journal	October 2006
A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms10101	journal	December 2015
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
Elastic Modulus of Isotopically-Concentrated Lithium Robertson, W. M.; Montgomery, D. J. Physical Review, Vol. 117, Issue 2 https://doi.org/10.1103/PhysRev.117.440	journal	January 1960
A novel PEO-based composite polymer electrolyte with absorptive glass mat for Li-ion batteries Tang, Zheng; Wang, Jianming; Chen, Quanqi Electrochimica Acta, Vol. 52, Issue 24 https://doi.org/10.1016/j.electacta.2007.04.062	journal	August 2007
Heat-resistant and rigid-flexible coupling glass-fiber nonwoven supported polymer electrolyte for high-performance lithium ion batteries Wang, Qingfu; Zhang, Bo; Zhang, Jianjun Electrochimica Acta, Vol. 157 https://doi.org/10.1016/j.electacta.2015.01.083	journal	March 2015
Cheap glass fiber mats as a matrix of gel polymer electrolytes for lithium ion batteries Zhu, Yusong; Wang, Faxing; Liu, Lili Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03187	journal	November 2013
Alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte for Zn–air battery Yang, Chun-Chen; Lin, Sheng-Jen Journal of Power Sources, Vol. 112, Issue 2 https://doi.org/10.1016/S0378-7753(02)00438-X	journal	November 2002
Polymeric gel electrolytes reinforced with glass-fibre cloth for lithium secondary batteries Park, Ho Cheol; Chun, Jong Han; Kim, Sang Hern Journal of Power Sources, Vol. 92, Issue 1-2 https://doi.org/10.1016/S0378-7753(00)00500-0	journal	January 2001
Solvent-Free Composite PEO-Ceramic Fiber/Mat Electrolytes for Lithium Secondary Cells Wang, Chunsheng; Zhang, Xiang-Wu; Appleby, A. John Journal of The Electrochemical Society, Vol. 152, Issue 1 https://doi.org/10.1149/1.1828952	journal	January 2005
LiFePO ₄ ‐Accelerated Change in Surface and Electrochemical Properties in Aqueous Systems Induced by Mechanical Agitation Geng, Linxiao; Foley, Sonia B.; Dong, Hongxu Energy Technology, Vol. 7, Issue 3 https://doi.org/10.1002/ente.201801116	journal	March 2019
High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation Schulze, Morgan W.; McIntosh, Lucas D.; Hillmyer, Marc A. Nano Letters, Vol. 14, Issue 1 https://doi.org/10.1021/nl4034818	journal	December 2013
Multifunctional Cross-Linked Polymeric Membranes for Safe, High-Performance Lithium Batteries Stalin, Sanjuna; Choudhury, Snehashis; Zhang, Kaihang Chemistry of Materials, Vol. 30, Issue 6 https://doi.org/10.1021/acs.chemmater.7b05353	journal	February 2018
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
Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries Pan, Qiwei; Smith, Derrick M.; Qi, Hao Advanced Materials, Vol. 27, Issue 39 https://doi.org/10.1002/adma.201502059	journal	August 2015
Polymer and composite electrolytes Hallinan, Daniel T.; Villaluenga, Irune; Balsara, Nitash P. MRS Bulletin, Vol. 43, Issue 10 https://doi.org/10.1557/mrs.2018.212	journal	October 2018
Highly-branched cross-linked poly(ethylene oxide) with enhanced ionic conductivity Paranjape, Nachiket; Mandadapu, Praphulla Chandra; Wu, Gang Polymer, Vol. 111 https://doi.org/10.1016/j.polymer.2017.01.014	journal	February 2017
Optimizing ionic conduction of poly(oxyethylene) electrolytes through controlling the cross-link density Thiam, Amdou; Antonelli, Claire; Iojoiu, Cristina Electrochimica Acta, Vol. 240 https://doi.org/10.1016/j.electacta.2017.04.046	journal	June 2017
Structure–property study of cross-linked hydrocarbon/poly(ethylene oxide) electrolytes with superior conductivity and dendrite resistance Zheng, Qi; Ma, Lin; Khurana, Rachna Chemical Science, Vol. 7, Issue 11 https://doi.org/10.1039/C6SC01813K	journal	January 2016
Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei Proceedings of the National Academy of Sciences, Vol. 113, Issue 1 https://doi.org/10.1073/pnas.1520394112	journal	December 2015
High Conductivity, High Strength Solid Electrolytes Formed by in Situ Encapsulation of Ionic Liquids in Nanofibrillar Methyl Cellulose Networks Mantravadi, Ramya; Chinnam, Parameswara Rao; Dikin, Dmitriy A. ACS Applied Materials & Interfaces, Vol. 8, Issue 21 https://doi.org/10.1021/acsami.6b02903	journal	May 2016
Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus Wang, Ying; Chen, Ying; Gao, Jianwei Advanced Materials, Vol. 28, Issue 13 https://doi.org/10.1002/adma.201505183	journal	January 2016
Polymer electrolytes for lithium polymer batteries Long, Lizhen; Wang, Shuanjin; Xiao, Min Journal of Materials Chemistry A, Vol. 4, Issue 26 https://doi.org/10.1039/C6TA02621D	journal	January 2016
A Close Look at the Structure of the TiO ₂ -APTES Interface in Hybrid Nanomaterials and Its Degradation Pathway: An Experimental and Theoretical Study Meroni, Daniela; Lo Presti, Leonardo; Di Liberto, Giovanni The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b10720	journal	December 2016
Molecular structures and normal vibrations of trifluoromethane sulfonate (CF3SO3-) and its lithium ion pairs and aggregates Huang, Weiwei; Frech, Roger; Wheeler, Ralph A. The Journal of Physical Chemistry, Vol. 98, Issue 1 https://doi.org/10.1021/j100052a018	journal	January 1994
Normal Vibrations of the Polymer Molecules of Helical Conformation. IV. Polyethylene Oxide and Polyethylene‐ d ₄ Oxide Yoshihara, Toshio; Tadokoro, Hiroyuki; Murahashi, Shunsuke The Journal of Chemical Physics, Vol. 41, Issue 9 https://doi.org/10.1063/1.1726373	journal	November 1964
Crystalline and Amorphous Phases in the Poly(ethylene oxide)−LiCF ₃ SO ₃ System Frech, Roger; Chintapalli, Sangramithra; Bruce, Peter G. Macromolecules, Vol. 32, Issue 3 https://doi.org/10.1021/ma9812682	journal	February 1999
Vibrational spectroscopy and structure of polymer electrolytes, poly(ethylene oxide) complexes of alkali metal salts Papke, B. L.; Ratner, M. A.; Shriver, D. F. Journal of Physics and Chemistry of Solids, Vol. 42, Issue 6 https://doi.org/10.1016/0022-3697(81)90030-5	journal	January 1981
Gold Nanoparticle Monolayers with Tunable Optical and Electrical Properties Yang, Guang; Hu, Longqian; Keiper, Timothy D. Langmuir, Vol. 32, Issue 16 https://doi.org/10.1021/acs.langmuir.6b00347	journal	April 2016
Conformation of poly(ethylene oxide) in the solid state, melt and solution measured by Raman scattering Maxfield, J.; Shepherd, I. W. Polymer, Vol. 16, Issue 7 https://doi.org/10.1016/0032-3861(75)90008-7	journal	July 1975
Electrolyte Solvation Structure at Solid–Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy Yang, Guang; Ivanov, Ilia N.; Ruther, Rose E. ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b05038	journal	September 2018
Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy Yang, Guang; Sacci, Robert L.; Ivanov, Ilia N. Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0391902jes	journal	January 2019
Resolution of the Modulus versus Adhesion Dilemma in Solid Polymer Electrolytes for Rechargeable Lithium Metal Batteries Stone, G. M.; Mullin, S. A.; Teran, A. A. Journal of The Electrochemical Society, Vol. 159, Issue 3 https://doi.org/10.1149/2.030203jes	journal	January 2012
Li ₇ La ₃ Zr ₂ O ₁₂ Interface Modification for Li Dendrite Prevention Tsai, Chih-Long; Roddatis, Vladimir; Chandran, C. Vinod ACS Applied Materials & Interfaces, Vol. 8, Issue 16 https://doi.org/10.1021/acsami.6b00831	journal	April 2016

Similar Records

Understanding the Influence of Li₇La₃Zr₂O₁₂ Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes

Journal Article · Fri May 19 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces · OSTI ID:1755308

Counihan, Michael J.; Powers, Devon J.; Barai, Pallab; +11 more

Novel Solvent-free Mg-ion Conducting Solid State Polymer Electrolyte

Technical Report · Tue Mar 29 00:00:00 EDT 2022 · OSTI ID:1755308

Tao, Greg; Kyu, Thein

A Silica-Aerogel-Reinforced Composite Polymer Electrolyte with High Ionic Conductivity and High Modulus

Journal Article · Mon Jun 25 00:00:00 EDT 2018 · Advanced Materials · OSTI ID:1755308

Lin, Dingchang; Yuen, Pak Yan; Liu, Yayuan; +4 more

Related Subjects

25 ENERGY STORAGE
lithium metal battery
composite polymer electrolytes
poly (ethylene oxide)
elastic modulus
machine learning
Raman mapping
K-means clustering

Title: Anomalously high elastic modulus of a poly(ethylene oxide)-based composite electrolyte

Citation Formats

References (53)

Similar Records

Related Subjects