Crosslinked perfluoropolyether solid electrolytes for lithium ion transport

Devaux, Didier; Villaluenga, Irune; Bhatt, Mahesh; Shah, Deep; Chen, X. Chelsea; Thelen, Jacob L.; DeSimone, Joseph M.; Balsara, Nitash P.

doi:10.1016/j.ssi.2017.08.007

Crosslinked perfluoropolyether solid electrolytes for lithium ion transport

Journal Article · Thu Aug 17 00:00:00 EDT 2017 · Solid State Ionics

DOI:https://doi.org/10.1016/j.ssi.2017.08.007· OSTI ID:1476567

^[1]; Villaluenga, Irune ^[1]; Bhatt, Mahesh ^[1]; ^[2]; Chen, X. Chelsea ^[3]; Thelen, Jacob L. ^[1]; DeSimone, Joseph M. ^[4]; Balsara, Nitash P. ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
University of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of North Carolina, Chapel Hill, NC (United States); North Carolina State University, Raleigh, NC (United States)

Perfluoropolyethers (PFPE) are commercially available non-flammable short chain polymeric liquids. End-functionalized PFPE chains solvate lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and these mixtures can be used as electrolytes for lithium (Li) batteries. Here we synthesize and characterize a new class of solid PFPE electrolytes. The electrolytes are made by either thermal or UV crosslinking PFPE chains with urethane methacrylate end-groups. For the synthesis of thermally crosslinked electrolytes, polyhedral oligomeric silsesquioxane (POSS) with organic acrylopropyl groups was used as crosslinker agent, while for UV cured electrolytes a photoinitiatior was used. We present thermal, morphological, and electrical data of the solid electrolytes. We compare these properties with those of the two parent liquids (PFPE with urethane methacrylate end-groups and POSS with acrylopropyl groups) mixed with LiTFSI. The solubility limit of LiTFSI in the PFPE-based solids is higher than that in the liquids. The conductivity data are analyzed using the Vogel–Tamman–Fulcher equation. In conclusion, the concentration of effective charge carriers is a strong function of the nature of the solvent (solid versus liquid) whereas the activation energy is neither a strong function of the nature of the solvent nor salt concentration.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES): National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1476567

Alternate ID(s):: OSTI ID: 1549859

Journal Information:: Solid State Ionics, Journal Name: Solid State Ionics Journal Issue: C Vol. 310; ISSN 0167-2738

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

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
Die Abhängigkeit der Viscosität von der Temperatur bie unterkühlten Flüssigkeiten Tammann, G.; Hesse, W. Zeitschrift für anorganische und allgemeine Chemie, Vol. 156, Issue 1 https://doi.org/10.1002/zaac.19261560121	journal	October 1926
Solid polymer electrolytes based on crosslinkable polyoctahedral silsesquioxanes (POSS) for room temperature lithium polymer batteries Lee, Jun Young; Lee, Yong Min; Bhattacharya, Bhaskar Journal of Solid State Electrochemistry, Vol. 14, Issue 8 https://doi.org/10.1007/s10008-009-0968-1	journal	November 2009
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
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
Reliability of lithium batteries with crosslinked polymer electrolytes Borghini, M. C.; Mastragostino, M.; Zanelli, A. Electrochimica Acta, Vol. 41, Issue 15 https://doi.org/10.1016/0013-4686(96)00014-X	journal	January 1996
Complexes of alkali metal ions with poly(ethylene oxide) Fenton, D. E.; Parker, J. M.; Wright, P. V. Polymer, Vol. 14, Issue 11 https://doi.org/10.1016/0032-3861(73)90146-8	journal	November 1973
Correlation among transport properties in ionically conducting cross-linked networks☆ Killis, A.; Lenest, J.; Gandini, A. Solid State Ionics, Vol. 14, Issue 3 https://doi.org/10.1016/0167-2738(84)90104-8	journal	November 1984
The effect of molecular weight on cation mobility in polymer electrolytes Shi, J.; Vincent, C. Solid State Ionics, Vol. 60, Issue 1-3 https://doi.org/10.1016/0167-2738(93)90268-8	journal	March 1993
The history of polymer electrolytes Armand, M. Solid State Ionics, Vol. 69, Issue 3-4 https://doi.org/10.1016/0167-2738(94)90419-7	journal	August 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
Salt-polymer complexes: strong or weak electrolytes? Souquet, J. Solid State Ionics, Vol. 85, Issue 1-4 https://doi.org/10.1016/0167-2738(96)00052-5	journal	May 1996
Ion–ion interactions and lithium stability in a crosslinked PEO containing lithium salts Laik, B.; Legrand, L.; Chausse, A. Electrochimica Acta, Vol. 44, Issue 5 https://doi.org/10.1016/S0013-4686(98)00247-3	journal	October 1998
Trends in polymer electrolytes for secondary lithium batteries Dias, Felix B.; Plomp, Lambertus; Veldhuis, Jakobert B. J. Journal of Power Sources, Vol. 88, Issue 2 https://doi.org/10.1016/S0378-7753(99)00529-7	journal	June 2000
Conductivity of carbonate- and perfluoropolyether-based electrolytes in porous separators Devaux, Didier; Chang, Yu H.; Villaluenga, Irune Journal of Power Sources, Vol. 323 https://doi.org/10.1016/j.jpowsour.2016.05.039	journal	August 2016
Preparation of solid-state composite electrolytes based on organic/inorganic hybrid star-shaped polymer and PEG-functionalized POSS for all-solid-state lithium battery applications Kim, Dong-Gyun; Shim, Jimin; Lee, Jin Hong Polymer, Vol. 54, Issue 21 https://doi.org/10.1016/j.polymer.2013.08.049	journal	October 2013
Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications Olson, Kevin R.; Wong, Dominica H. C.; Chintapalli, Mahati Polymer, Vol. 100 https://doi.org/10.1016/j.polymer.2016.08.020	journal	September 2016
POSS related polymer nanocomposites Kuo, Shiao-Wei; Chang, Feng-Chih Progress in Polymer Science, Vol. 36, Issue 12 https://doi.org/10.1016/j.progpolymsci.2011.05.002	journal	December 2011
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups Devaux, D.; Bouchet, R.; Glé, D. Solid State Ionics, Vol. 227 https://doi.org/10.1016/j.ssi.2012.09.020	journal	October 2012
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
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
Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M. ACS Central Science, Vol. 1, Issue 4 https://doi.org/10.1021/acscentsci.5b00195	journal	July 2015
Oligomeric Poly(ethylene oxide)-Functionalized Silsesquioxanes: Interfacial Effects on T _g , T _m , and Δ H _m Maitra, Prithwiraj; Wunder, Stephanie L. Chemistry of Materials, Vol. 14, Issue 11 https://doi.org/10.1021/cm0203518	journal	October 2002
Electrochemical and Mechanical Behavior in Mechanically Robust Solid Polymer Electrolytes for Use in Multifunctional Structural Batteries Snyder, James F.; Carter, Robert H.; Wetzel, Eric D. Chemistry of Materials, Vol. 19, Issue 15 https://doi.org/10.1021/cm070213o	journal	July 2007
Polyoctahedral Silsesquioxane-Nanoparticle Electrolytes for Lithium Batteries: POSS-Lithium Salts and POSS-PEGs Chinnam, Parameswara Rao; Wunder, Stephanie L. Chemistry of Materials, Vol. 23, Issue 23 https://doi.org/10.1021/cm2015675	journal	December 2011
Phase Behavior and Electrochemical Characterization of Blends of Perfluoropolyether, Poly(ethylene glycol), and a Lithium Salt Wong, Dominica H. C.; Vitale, Alessandra; Devaux, Didier Chemistry of Materials, Vol. 27, Issue 2 https://doi.org/10.1021/cm504228a	journal	January 2015
Recent Developments in the Chemistry of Cubic Polyhedral Oligosilsesquioxanes Cordes, David B.; Lickiss, Paul D.; Rataboul, Franck Chemical Reviews, Vol. 110, Issue 4 https://doi.org/10.1021/cr900201r	journal	April 2010
POSS Ionic Liquid Tanaka, Kazuo; Ishiguro, Fumiyasu; Chujo, Yoshiki Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja105631j	journal	December 2010
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
The Influence of Inert Oxide Fillers on Poly(ethylene oxide) and Amorphous Poly(ethylene oxide) Based Polymer Electrolytes ^† Johansson, Patrik; Ratner, Mark A.; Shriver, Duward F. The Journal of Physical Chemistry B, Vol. 105, Issue 37 https://doi.org/10.1021/jp010868r	journal	September 2001
Blends of POSS−PEO( n =4) ₈ and High Molecular Weight Poly(ethylene oxide) as Solid Polymer Electrolytes for Lithium Batteries Zhang, Hanjun; Kulkarni, Sunil; Wunder, Stephanie L. The Journal of Physical Chemistry B, Vol. 111, Issue 14 https://doi.org/10.1021/jp064585g	journal	April 2007
Photocurable Silsesquioxane-Based Formulations as Versatile Resins for Nanoimprint Lithography Lee, Bong Kuk; Cha, Nam-Goo; Hong, Lan-Young Langmuir, Vol. 26, Issue 18 https://doi.org/10.1021/la1025119	journal	September 2010
Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes Lascaud, S.; Perrier, M.; Vallee, A. Macromolecules, Vol. 27, Issue 25 https://doi.org/10.1021/ma00103a034	journal	December 1994
Photochemically Cross-Linked Perfluoropolyether-Based Elastomers: Synthesis, Physical Characterization, and Biofouling Evaluation Hu, Zhaokang; Finlay, John A.; Chen, Liang Macromolecules, Vol. 42, Issue 18, p. 6999-7007 https://doi.org/10.1021/ma901227k	journal	September 2009
High-Resolution PFPE-based Molding Techniques for Nanofabrication of High-Pattern Density, Sub-20 nm Features: A Fundamental Materials Approach Williams, Stuart S.; Retterer, Scott; Lopez, Rene Nano Letters, Vol. 10, Issue 4 https://doi.org/10.1021/nl100326q	journal	February 2010
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
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Self-assembled Janus-like multi-ionic lithium salts form nano-structured solid polymer electrolytes with high ionic conductivity and Li ⁺ ion transference number Chinnam, Parameswara Rao; Wunder, Stephanie L. J. Mater. Chem. A, Vol. 1, Issue 5 https://doi.org/10.1039/C2TA00085G	journal	January 2013
Poly(ethylene oxide)-based electrolytes for lithium-ion batteries Xue, Zhigang; He, Dan; Xie, Xiaolin Journal of Materials Chemistry A, Vol. 3, Issue 38 https://doi.org/10.1039/C5TA03471J	journal	January 2015
Thermodynamics of High Polymer Solutions Flory, Paul J. The Journal of Chemical Physics, Vol. 10, Issue 1 https://doi.org/10.1063/1.1723621	journal	January 1942
Solutions of Long Chain Compounds Huggins, Maurice L. The Journal of Chemical Physics, Vol. 9, Issue 5 https://doi.org/10.1063/1.1750930	journal	May 1941
Nonflammable perfluoropolyether-based electrolytes for lithium batteries Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao Proceedings of the National Academy of Sciences, Vol. 111, Issue 9 https://doi.org/10.1073/pnas.1314615111	journal	February 2014
Analysis of Recent Measurements of the Viscosity of Glasses Fulcher, Gordon S. Journal of the American Ceramic Society, Vol. 8, Issue 6 https://doi.org/10.1111/j.1151-2916.1925.tb16731.x	journal	June 1925
POSS Based Electrolytes for Rechargeable Lithium Batteries Maitra, Prithwiraj; Wunder, Stephanie L. Electrochemical and Solid-State Letters, Vol. 7, Issue 4 https://doi.org/10.1149/1.1646832	journal	January 2004
Network Polymer Electrolytes with Free Chain Ends as Internal Plasticizer Kono, Michiyuki; Hayashi, Eriko; Watanabe, Masayoshi Journal of The Electrochemical Society, Vol. 145, Issue 5 https://doi.org/10.1149/1.1838514	journal	May 1998
Analysis of Transference Number Measurements Based on the Potentiostatic Polarization of Solid Polymer Electrolytes Doyle, Marc Journal of The Electrochemical Society, Vol. 142, Issue 10 https://doi.org/10.1149/1.2050005	journal	January 1995
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
Polyethylene Glycol Functionalized Polyoctahedral Silsesquioxanes as Electrolytes for Lithium Batteries Zhang, Hanjun; Kulkarni, Sunil; Wunder, Stephanie L. Journal of The Electrochemical Society, Vol. 153, Issue 2 https://doi.org/10.1149/1.2139869	journal	January 2006

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Crosslinked perfluoropolyether solid electrolytes for lithium ion transport

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