Tailored crosslinking of Poly(ethylene oxide) enables mechanical robustness and improved sodium-ion conductivity

Lehmann, Michelle L.; Yang, Guang; Gilmer, Dustin B.; Han, Kee Sung; Self, Ethan C.; Ruther, Rose E.; Ge, Sirui; Li, Bingrui; Murugesan, Vijayakumar; Sokolov, Alexei P.; Delnick, Frank M.; Nanda, Jagjit; Saito, Tomonori

doi:10.1016/j.ensm.2019.06.028

Title: Tailored crosslinking of Poly(ethylene oxide) enables mechanical robustness and improved sodium-ion conductivity

Journal Article · 20 June 2019 · Energy Storage Materials

DOI: https://doi.org/10.1016/j.ensm.2019.06.028 · OSTI ID:1558567

Lehmann, Michelle L. ^[1];

^[2]; Gilmer, Dustin B. ^[1]; Han, Kee Sung ^[3];

^[2];

^[2]; Ge, Sirui ^[4];

^[1]; Murugesan, Vijayakumar ^[3];

^[1];

^[2];

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Tennessee, Knoxville, TN (United States)

We report that sodium-based energy storage systems are promising candidates for electric vehicles and grid-level energy storage applications. The advancement of sodium-based energy storage systems relies on the development of high performance sodium-ion conducting electrolytes and membranes that exhibit high ionic conductivity and mechanical stability. A crosslinked poly(ethylene oxide) based polymer electrolyte was developed that demonstrates high ionic conductivity, as well as excellent mechanical stability over a wide temperature range. Ionic conductivities up to 2.0 × 10^-4 S/cm at 20 °C and 7.1 × 10^-4 S/cm at 70 °C are achieved for the plasticized membrane, almost four orders of magnitude greater than that of the non-plasticized membrane. The membranes are mechanically robust, and the storage modulus of the membrane is maintained at ~1 MPa from -20 to 180 °C even with the addition of plasticizer. In conclusion, this study provides a synthesis approach towards the design of highly ion conducting, mechanically robust gel polymer electrolytes for Na-ion batteries, non-aqueous flow batteries, and many other applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725; AC05-76RL01830

OSTI ID:: 1558567

Report Number(s):: PNNL-SA-146061

Journal Information:: Energy Storage Materials, Journal Name: Energy Storage Materials Vol. 21; ISSN 2405-8297

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Photopolymer Electrolytes for Sustainable, Upscalable, Safe, and Ambient-Temperature Sodium-Ion Secondary Batteries Bella, Federico; Colò, Francesca; Nair, Jijeesh R. ChemSusChem, Vol. 8, Issue 21 https://doi.org/10.1002/cssc.201500873	journal	October 2015
A Raman study of ion solvation and association in polymer electrolytes Torell, Lena M.; Jacobsson, Per; Petersen, Greger Polymers for Advanced Technologies, Vol. 4, Issue 23 https://doi.org/10.1002/pat.1993.220040215	journal	February 1993
Vibrational analysis of molten poly(ethylene glycol) Matsuura, Hiroatsu; Miyazawa, Tatsuo Journal of Polymer Science Part A-2: Polymer Physics, Vol. 7, Issue 10 https://doi.org/10.1002/pol.1969.160071009	journal	October 1969
Raman spectra of poly(ethylene glycols) in solution Koenig, J. L.; Angood, A. C. Journal of Polymer Science Part A-2: Polymer Physics, Vol. 8, Issue 10 https://doi.org/10.1002/pol.1970.160081013	journal	October 1970
Conductivity studies on PEO:NaClO3 electrolyte system with different plasticizers Chandrasekaran, R.; Ruth Mangani, I.; Vasanthi, R. Ionics, Vol. 7, Issue 1-2 https://doi.org/10.1007/BF02375473	journal	January 2001
Effect of plasticizer on structural and electrical properties of nanocomposite solid polymer electrolytes Pradhan, Dillip K.; Samantaray, B. K.; Choudhary, R. N. P. Ionics, Vol. 17, Issue 2 https://doi.org/10.1007/s11581-010-0491-5	journal	December 2010
A Raman study of ion—polymer and ion—ion interactions in low molecular weight polyether—LiCF3SO3 complexes Petersen, G.; Jacobsson, P.; Torell, L. M. Electrochimica Acta, Vol. 37, Issue 9 https://doi.org/10.1016/0013-4686(92)80097-6	journal	January 1992
A new polymer network for ionic conduction Le Nest, J. F.; Callens, S.; Gandini, A. Electrochimica Acta, Vol. 37, Issue 9 https://doi.org/10.1016/0013-4686(92)80116-4	journal	January 1992
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
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
Electrochemical measurement of transference numbers in polymer electrolytes Evans, James; Vincent, Colin A.; Bruce, Peter G. Polymer, Vol. 28, Issue 13 https://doi.org/10.1016/0032-3861(87)90394-6	journal	December 1987
The structure of associated ionic species in poly(propylene oxide)-alkali metal trifluoromethanesulphonate complexes Manning, John; Frech, Roger Polymer, Vol. 33, Issue 16 https://doi.org/10.1016/0032-3861(92)91108-E	journal	January 1992
Microscopic investigation of ionic conductivity in alkali metal salts-poly(ethylene oxide) adducts Berthier, C.; Gorecki, W.; Minier, M. Solid State Ionics, Vol. 11, Issue 1 https://doi.org/10.1016/0167-2738(83)90068-1	journal	September 1983
A new Na+ ion conducting polymer electrolyte based on (PEO+NaYF4) and its use as an electrochemical cell Sreepathirao, S.; Jaipalreddy, M.; Narasimhareddy, K. Solid State Ionics, Vol. 74, Issue 3-4 https://doi.org/10.1016/0167-2738(94)90214-3	journal	December 1994
Effects of network structures and incorporated salt species on electrochemical properties of polyether-based polymer electrolytes Watanabe, M. Solid State Ionics, Vol. 79 https://doi.org/10.1016/0167-2738(95)00079-L	journal	July 1995
Experimental investigations on a sodium-ion-conducting polymer electrolyte based on poly(ethylene oxide) complexed with NaPF6 Hashmi, S. A.; Chandra, S. Materials Science and Engineering: B, Vol. 34, Issue 1 https://doi.org/10.1016/0921-5107(95)01219-2	journal	October 1995
Cationâanion and cationâpolymer interactions in (PEO)nNaCF3SO3 (n=1â80) Rhodes, C. Solid State Ionics, Vol. 121, Issue 1-4 https://doi.org/10.1016/S0167-2738(98)00534-7	journal	June 1999
Investigation on solvent-free solid polymer electrolytes for advanced lithium batteries and their performance Aihara, Y.; Kuratomi, J.; Bando, T. Journal of Power Sources, Vol. 114, Issue 1 https://doi.org/10.1016/S0378-7753(02)00529-3	journal	February 2003
A study of cross-linked PEO gel polymer electrolytes using bisphenol A ethoxylate diacrylate: ionic conductivity and mechanical properties Kang, Yongku; Cheong, Kwangjo; Noh, Kun-Ae Journal of Power Sources, Vol. 119-121 https://doi.org/10.1016/S0378-7753(03)00183-6	journal	June 2003
IONIC CONDUCTIVITY AND LITHIUM TRANSFERENCE NUMBER OF POLY(ETHYLENE OXIDE):LiTFSI SYSTEM Pożyczka, K.; Marzantowicz, M.; Dygas, J. R. Electrochimica Acta, Vol. 227 https://doi.org/10.1016/j.electacta.2016.12.172	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
Energy storage materials: A perspective Goodenough, John B. Energy Storage Materials, Vol. 1 https://doi.org/10.1016/j.ensm.2015.07.001	journal	November 2015
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
Polymer electrolyte for lithium batteries based on photochemically crosslinked poly(ethylene oxide) and ionic liquid Rupp, Barbara; Schmuck, Martin; Balducci, Andrea European Polymer Journal, Vol. 44, Issue 9 https://doi.org/10.1016/j.eurpolymj.2008.06.022	journal	September 2008
Solid-state dye-sensitized solar cell: Improved performance and stability using a plasticized polymer electrolyte Nogueira, Viviane C.; Longo, Claudia; Nogueira, Ana Flávia Journal of Photochemistry and Photobiology A: Chemistry, Vol. 181, Issue 2-3 https://doi.org/10.1016/j.jphotochem.2005.11.028	journal	July 2006
Effect of plasticizer on structure—property relationship in composite polymer electrolytes Pradhan, Dillip K.; Samantaray, B. K.; Choudhary, R. N. P. Journal of Power Sources, Vol. 139, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2004.05.050	journal	January 2005
UV cross-linked, lithium-conducting ternary polymer electrolytes containing ionic liquids Kim, G. T.; Appetecchi, G. B.; Carewska, M. Journal of Power Sources, Vol. 195, Issue 18 https://doi.org/10.1016/j.jpowsour.2009.10.079	journal	September 2010
Thermal runaway caused fire and explosion of lithium ion battery Wang, Qingsong; Ping, Ping; Zhao, Xuejuan Journal of Power Sources, Vol. 208 https://doi.org/10.1016/j.jpowsour.2012.02.038	journal	June 2012
Composite PEOn:NaTFSI polymer electrolyte: Preparation, thermal and electrochemical characterization Serra Moreno, J.; Armand, M.; Berman, M. B. Journal of Power Sources, Vol. 248 https://doi.org/10.1016/j.jpowsour.2013.09.137	journal	February 2014
Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor Chaudoy, V.; Tran Van, F.; Deschamps, M. Journal of Power Sources, Vol. 342 https://doi.org/10.1016/j.jpowsour.2016.12.097	journal	February 2017
Light-cured polymer electrolytes for safe, low-cost and sustainable sodium-ion batteries Colò, Francesca; Bella, Federico; Nair, Jijeesh R. Journal of Power Sources, Vol. 365 https://doi.org/10.1016/j.jpowsour.2017.08.079	journal	October 2017
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
Crosslinked poly(acrylonitrile–glycidyl methacrylate) as a novel gel polymer electrolyte Luo, Dan; Li, Yang; Yang, Mujie Materials Chemistry and Physics, Vol. 125, Issue 1-2 https://doi.org/10.1016/j.matchemphys.2010.09.012	journal	January 2011
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
All-solid-state lithium metal battery with solid polymer electrolytes based on polysiloxane crosslinked by modified natural gallic acid Shim, Jimin; Kim, Lucia; Kim, Hee Joong Polymer, Vol. 122 https://doi.org/10.1016/j.polymer.2017.06.074	journal	July 2017
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
Relationship between Conductivity, Ion Diffusion, and Transference Number in Perfluoropolyether Electrolytes Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R. Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.6b00412	journal	April 2016
Effect of Plasticization on Ionic Conductivity Enhancement in Relation to Glass Transition Temperature of Crosslinked Polymer Electrolyte Membranes He, Ruixuan; Kyu, Thein Macromolecules, Vol. 49, Issue 15 https://doi.org/10.1021/acs.macromol.6b00918	journal	July 2016
Comparative Study of Ether-Based Electrolytes for Application in Lithium–Sulfur Battery Carbone, Lorenzo; Gobet, Mallory; Peng, Jing ACS Applied Materials & Interfaces, Vol. 7, Issue 25 https://doi.org/10.1021/acsami.5b02160	journal	June 2015
Stable Lithium Deposition Generated from Ceramic-Cross-Linked Gel Polymer Electrolytes for Lithium Anode Tsao, Chih-Hao; Hsiao, Yang-Hung; Hsu, Chun-Han ACS Applied Materials & Interfaces, Vol. 8, Issue 24 https://doi.org/10.1021/acsami.6b02345	journal	June 2016
A Highly Reversible Room-Temperature Sodium Metal Anode Seh, Zhi Wei; Sun, Jie; Sun, Yongming ACS Central Science, Vol. 1, Issue 8 https://doi.org/10.1021/acscentsci.5b00328	journal	November 2015
Rechargeable Sodium All-Solid-State Battery Zhou, Weidong; Li, Yutao; Xin, Sen ACS Central Science, Vol. 3, Issue 1 https://doi.org/10.1021/acscentsci.6b00321	journal	January 2017
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
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
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
Crystalline Phases of Poly(Ethylene Oxide) Oligomers and Sodium Triflate: Changes in Coordination and Conformation with Chain Length Rhodes, Christopher P.; Khan, Masood; Frech, Roger The Journal of Physical Chemistry B, Vol. 106, Issue 40 https://doi.org/10.1021/jp0141981	journal	October 2002
¹³ C NMR Relaxation and ¹ H Diffusion (DOSY) Studies of an Acidic Chloroaluminate Melt Carper, W. Robert; Mains, Gilbert J.; Piersma, Bernard J. The Journal of Physical Chemistry, Vol. 100, Issue 12 https://doi.org/10.1021/jp953199o	journal	January 1996
Direct Determination of NMR Correlation Times from Spin−Lattice and Spin−Spin Relaxation Times Carper, W. Robert; Keller, Charles E. The Journal of Physical Chemistry A, Vol. 101, Issue 18 https://doi.org/10.1021/jp963338h	journal	May 1997
Nature and Dynamics of Lithium Ion Coordination in Oligo(ethylene glycol) Dimethacrylate-Solvent Systems: NMR, Raman, and Quantum Mechanical Study Kříž, J.; Abbrent, S.; Dybal, J. The Journal of Physical Chemistry A, Vol. 103, Issue 42 https://doi.org/10.1021/jp991410g	journal	September 1999
Synthesis and Characterization of Network Type Single Ion Conductors Sun, Xiao-Guang; Reeder, Craig L.; Kerr, John B. Macromolecules, Vol. 37, Issue 6 https://doi.org/10.1021/ma035690g	journal	March 2004
A 3.8-V earth-abundant sodium battery electrode Barpanda, Prabeer; Oyama, Gosuke; Nishimura, Shin-ichi Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5358	journal	July 2014
Ultrastructural Characterization of the Lower Motor System in a Mouse Model of Krabbe Disease Cappello, Valentina; Marchetti, Laura; Parlanti, Paola Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/s41598-016-0001-8	journal	December 2016
A hybrid solid electrolyte for flexible solid-state sodium batteries Kim, Jae-Kwang; Lim, Young Jun; Kim, Hyojin Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE01941A	journal	January 2015
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
Electrolyte design strategies and research progress for room-temperature sodium-ion batteries Che, Haiying; Chen, Suli; Xie, Yingying Energy & Environmental Science, Vol. 10, Issue 5 https://doi.org/10.1039/C7EE00524E	journal	January 2017
A new Na[(FSO ₂ )(n-C ₄ F ₉ SO ₂ )N]-based polymer electrolyte for solid-state sodium batteries Ma, Qiang; Liu, Juanjuan; Qi, Xingguo Journal of Materials Chemistry A, Vol. 5, Issue 17 https://doi.org/10.1039/C7TA01820G	journal	January 2017
Na-ion batteries, recent advances and present challenges to become low cost energy storage systems Palomares, Verónica; Serras, Paula; Villaluenga, Irune Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee02781j	journal	January 2012
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
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
Electrochemical Behavior of Lithium Electrolytes Based on New Polyether Networks Alloin, F.; Sanchez, J. ‐Y.; Armand, M. Journal of The Electrochemical Society, Vol. 141, Issue 7 https://doi.org/10.1149/1.2055026	journal	July 1994
Dendrite-Free Electrodeposition and Reoxidation of Lithium-Sodium Alloy for Metal-Anode Battery Stark, Johanna K.; Ding, Yi; Kohl, Paul A. Journal of The Electrochemical Society, Vol. 158, Issue 10 https://doi.org/10.1149/1.3622348	journal	January 2011
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

Similar Records

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

Journal Article · 2020 · Energy Storage Materials · OSTI ID:1755308

Yang, Guang; Lehmann, Michelle L.; Zhao, Sheng; +7 more

Plasticizer-Free Gradient-Crosslinked Polyurethane Electrolyte for Room-Temperature Solid-State Lithium Batteries

Journal Article · 2026 · Journal of the Electrochemical Society · OSTI ID:3377344

Wang, Nan; Yen, Dean; Zhang, Xiaohu; +5 more

Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO{sub 4} for lithium ion battery application

Journal Article · 2015 · AIP Conference Proceedings · OSTI ID:22488925

Nurhadini,

Related Subjects

25 ENERGY STORAGE
Conductivity
Mechanical robustness
Poly(ethylene oxide)
Polymer electrolyte
Sodium-ion battery

Title: Tailored crosslinking of Poly(ethylene oxide) enables mechanical robustness and improved sodium-ion conductivity

Citation Formats

References (62)

Similar Records

Related Subjects