Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications

Olson, Kevin R.; Wong, Dominica H. C.; Chintapalli, Mahati; Timachova, Ksenia; Janusziewicz, Rima; Daniel, William F. M.; Mecham, Sue; Sheiko, Sergei; Balsara, Nitash P.; DeSimone, Joseph M.

doi:10.1016/j.polymer.2016.08.020

Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications

Journal Article · Mon Aug 08 00:00:00 EDT 2016 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2016.08.020· OSTI ID:1474966

Olson, Kevin R. ^[1]; Wong, Dominica H. C. ^[1]; Chintapalli, Mahati ^[2]; Timachova, Ksenia ^[2]; Janusziewicz, Rima ^[1]; Daniel, William F. M. ^[1]; Mecham, Sue ^[1]; Sheiko, Sergei ^[1]; Balsara, Nitash P. ^[3]; DeSimone, Joseph M. ^[4]

University of North Carolina, Chapel Hill, NC (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)

Here, we prepared nonflammable liquid polymer electrolytes for lithium-ion batteries by mixing ethoxylated perfluoropolyethers (PFPEs) with LiN(SO₂CF₃)₂ salt. Interestingly, we identified the presence of chain coupling in the PFPE polymers and their functionalized derivatives, resulting in a mixture of PFPEs with varying molecular weights. The distribution of molecular weights, along with PFPE's multiple functionalities, allows systematic manipulation of structure to enhance electrochemical and physical properties. Furthermore, the electrolytes exhibited a wide thermal stability window (5% degradation temperature >180°C). Despite substantial increases in viscosity upon loading the PFPEs with lithium salt, the conductivity (σ ≈ 5 × 10^-5 S cm^-1 at 28°C) of the novel electrolytes was about an order of magnitude higher than that of our previously reported PFPE electrolytes. Ethoxylated derivatives of PFPE electrolytes exhibit elevated conductivity compared to non-ethoxylated derivatives, demonstrating our capability to enhance the conductive properties of the PFPE platform by attaching various functional groups to the polymer backbone.

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); Stony Brook Univ., NY (United States). Center for Mesoscale Transport Properties (m2M)

Grant/Contract Number:: AC02-05CH11231; SC0012673

OSTI ID:: 1474966

Alternate ID(s):: OSTI ID: 1359789

Journal Information:: Polymer, Journal Name: Polymer Journal Issue: C Vol. 100; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Functional Materials for Rechargeable Batteries Cheng, Fangyi; Liang, Jing; Tao, Zhanliang Advanced Materials, Vol. 23, Issue 15 https://doi.org/10.1002/adma.201003587	journal	March 2011
Interactions of inorganic salts with poly(ethylene oxide) Lundberg, R. D.; Bailey, F. E.; Callard, R. W. Journal of Polymer Science Part A-1: Polymer Chemistry, Vol. 4, Issue 6 https://doi.org/10.1002/pol.1966.150040620	journal	June 1966
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
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
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
Lithium ionic conduction in poly (methacrylic acid)-poly (ethylene oxide) complex containing lithium perchlorate Tsuchida, E.; Ohno, H.; Tsunemi, K. Solid State Ionics, Vol. 11, Issue 3 https://doi.org/10.1016/0167-2738(83)90028-0	journal	November 1983
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
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
Linear perfluoropolyether difunctional oligomers: chemistry, properties and applications Tonelli, Claudio; Gavezotti, Piero; Strepparola, Ezio Journal of Fluorine Chemistry, Vol. 95, Issue 1-2, p. 51-70 https://doi.org/10.1016/S0022-1139(98)00298-X	journal	June 1999
Mixed solvent electrolytes containing fluorinated carboxylic acid esters to improve the thermal stability of lithium metal anode cells Sato, K. Solid State Ionics, Vol. 148, Issue 3-4 https://doi.org/10.1016/S0167-2738(02)00088-7	journal	June 2002
No-flash-point electrolytes applied to amorphous carbon/Li1+xMn2O4 cells for EV use Arai, Juichi Journal of Power Sources, Vol. 119-121 https://doi.org/10.1016/S0378-7753(03)00258-1	journal	June 2003
Influence of crystalline complexes on electrical properties of PEO:LiTFSI electrolyte Marzantowicz, M.; Dygas, J. R.; Krok, F. Electrochimica Acta, Vol. 53, Issue 4 https://doi.org/10.1016/j.electacta.2007.03.032	journal	December 2007
Redox shuttles for safer lithium-ion batteries Chen, Zonghai; Qin, Yan; Amine, Khalil Electrochimica Acta, Vol. 54, Issue 24, p. 5605-5613 https://doi.org/10.1016/j.electacta.2009.05.017	journal	October 2009
Thermal runaway inhibitors for lithium battery electrolytes Mandal, Braja K.; Padhi, Akshaya K.; Shi, Zhong Journal of Power Sources, Vol. 161, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.06.008	journal	October 2006
Comparative study of EC/DMC LiTFSI and LiPF6 electrolytes for electrochemical storage Dahbi, Mouad; Ghamouss, Fouad; Tran-Van, François Journal of Power Sources, Vol. 196, Issue 22 https://doi.org/10.1016/j.jpowsour.2011.07.071	journal	November 2011
PEI–LiTFSI electrolytes for electrochromic devices: Characterization by differential scanning calorimetry and viscosity measurements Pehlivan, İlknur Bayrak; Marsal, Roser; Niklasson, Gunnar A. Solar Energy Materials and Solar Cells, Vol. 94, Issue 12 https://doi.org/10.1016/j.solmat.2010.08.025	journal	December 2010
Effect of molecular weight on conductivity of polymer electrolytes Teran, Alexander A.; Tang, Maureen H.; Mullin, Scott A. Solid State Ionics, Vol. 203, Issue 1 https://doi.org/10.1016/j.ssi.2011.09.021	journal	November 2011
Synthetic applications of fluorous solid-phase extraction (F-SPE) Zhang, Wei; Curran, Dennis P. Tetrahedron, Vol. 62, Issue 51 https://doi.org/10.1016/j.tet.2006.08.051	journal	December 2006
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
Engineering Protein Stability and Specificity Using Fluorous Amino Acids: The Importance of Packing Effects Buer, Benjamin C.; de la Salud-Bea, Roberto; Al Hashimi, Hashim M. Biochemistry, Vol. 48, Issue 45 https://doi.org/10.1021/bi901481k	journal	November 2009
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
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Influence of ion pairing on cation transport in the polymer electrolytes formed by poly(ethylene oxide) with sodium tetrafluoroborate and sodium tetrahydroborate Dupon, R.; Papke, B. L.; Ratner, M. A. Journal of the American Chemical Society, Vol. 104, Issue 23 https://doi.org/10.1021/ja00387a014	journal	November 1982
Fluorous-Based Carbohydrate Microarrays Ko, Kwang-Seuk; Jaipuri, Firoz A.; Pohl, Nicola L. Journal of the American Chemical Society, Vol. 127, Issue 38 https://doi.org/10.1021/ja054811k	journal	September 2005
Modulating Protein Structure with Fluorous Amino Acids: Increased Stability and Native-like Structure Conferred on a 4-Helix Bundle Protein by Hexafluoroleucine Lee, Hyang-Yeol; Lee, Kyung-Hoon; Al-Hashimi, Hashim M. Journal of the American Chemical Society, Vol. 128, Issue 1 https://doi.org/10.1021/ja0563410	journal	January 2006
The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
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
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
Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes Sun, Jing; Stone, Gregory M.; Balsara, Nitash P. Macromolecules, Vol. 45, Issue 12 https://doi.org/10.1021/ma300775b	journal	June 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
Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries Barteau, Katherine P.; Wolffs, Martin; Lynd, Nathaniel A. Macromolecules, Vol. 46, Issue 22 https://doi.org/10.1021/ma401267w	journal	November 2013
Salt-Concentration Dependence of the Glass Transition Temperature in PEO–NaI and PEO–LiTFSI Polymer Electrolytes Stolwijk, Nicolaas A.; Heddier, Christian; Reschke, Manuel Macromolecules, Vol. 46, Issue 21 https://doi.org/10.1021/ma401686r	journal	October 2013
Structure of the polymer electrolyte poly(ethylene oxide)6:LiAsF6 MacGlashan, Graham S.; Andreev, Yuri G.; Bruce, Peter G. Nature, Vol. 398, Issue 6730 https://doi.org/10.1038/19730	journal	April 1999
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
The fluorous effect in biomolecular applications Cametti, Massimo; Crousse, Benoit; Metrangolo, Pierangelo Chem. Soc. Rev., Vol. 41, Issue 1 https://doi.org/10.1039/C1CS15084G	journal	January 2012
Activation of transport and local dynamics in polysiloxane-based salt-in-polymer electrolytes: a multinuclear NMR study Kunze, Miriam; Karatas, Yunus; Wiemhöfer, Hans-Dieter Physical Chemistry Chemical Physics, Vol. 12, Issue 25 https://doi.org/10.1039/b925840j	journal	January 2010
Structure of the polymer electrolyte poly(ethylene oxide)3: LiN(SO2CF3)2 determined by powder diffraction using a powerful Monte Carlo approach Andreev, Y. G.; Lightfoot, P.; Bruce, P. G. Chemical Communications, Issue 18 https://doi.org/10.1039/cc9960002169	journal	January 1996
Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight Fox, Thomas G.; Flory, Paul J. Journal of Applied Physics, Vol. 21, Issue 6 https://doi.org/10.1063/1.1699711	journal	June 1950
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
Crystal Structure of the Polymer Electrolyte Poly(ethylene oxide)3:LiCF3SO3 Lightfoot, P.; Mehta, M. A.; Bruce, P. G. Science, Vol. 262, Issue 5135 https://doi.org/10.1126/science.262.5135.883	journal	November 1993
Polymer Electrolytes Armand, Michel B. Annual Review of Materials Science, Vol. 16, Issue 1 https://doi.org/10.1146/annurev.ms.16.080186.001333	journal	August 1986
Solvation of Lithium Ions in Mixed Organic Electrolyte Solutions by Electrospray Ionization Mass Spectroscopy Matsuda, Yoshiharu; Fukushima, Tsuyoshi; Hashimoto, Hiroyuki Journal of The Electrochemical Society, Vol. 149, Issue 8 https://doi.org/10.1149/1.1489687	journal	January 2002
Binding of Ether and Carbonyl Oxygens to Lithium Ion Blint, Richard J. Journal of The Electrochemical Society, Vol. 142, Issue 3 https://doi.org/10.1149/1.2048519	journal	January 1995
Electrolyte Solvation and Ionic Association III. Acetonitrile-Lithium Salt Mixtures–Transport Properties Seo, Daniel M.; Borodin, Oleg; Balogh, Daniel Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.018308jes	journal	January 2013

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