Dependence of Linker Length and Composition on Ionic Conductivity and Lithium Deposition in Single-Ion Conducting Network Polymers

Aubrey, Michael L.; Axelson, Jordan C.; Engler, Kaitlyn E.; Long, Jeffrey R.

doi:10.1021/acs.macromol.1c00911

Title: Dependence of Linker Length and Composition on Ionic Conductivity and Lithium Deposition in Single-Ion Conducting Network Polymers

Journal Article · 08 August 2021 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.1c00911 · OSTI ID:1843007

Aubrey, Michael L. ^[1]; Axelson, Jordan C. ^[1]; Engler, Kaitlyn E. ^[1];

^[2]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

In this report, single-ion conducting electrolytes stand as promising alternatives to state-of-the-Art electrolytes in lithium batteries, although a single-ion conducting material with high Li⁺ conductivity, stability in contact with lithium, and suitable mechanical properties has been slow to emerge. Here, we describe the synthesis of a series of single-ion conducting network polymers from the reaction of tetrakis(4-(chloromethyl)-2,3,5,6-Tetrafluorophenyl)borate with oligoethylene glycoxide linkers Li₂O[(CH₂CH₂)O]_n (n = 1, 2, 3, 9, and 22). Polymers with the longest linkers (n = 9 and 22; ANP-9 and ANP-10, respectively) form materials with conductivities of ~ 10^-6 S cm^-1 at 100 °C. With the addition of 65 wt % propylene carbonate (PC), all the network polymers in the series exhibit high conductivities at ambient temperatures, with the n = 1 material (ANP-6) achieving a bulk ionic conductivity of 2.5 x 10^-4 S cm^-1 at 25 °C. More conductive single-ion conducting gels could be prepared by using the less coordinating pentanediol dilithium salt as a linker (ANP-11; σ = 3.5 x 10^-4 S cm^-1 at 25 °C), although this material exhibited a surprisingly high interfacial resistance in contact with a lithium electrode. In contrast, the gel formed with ANP-6 is notably stable in contact with metallic lithium electrodes, displays a lithium-ion transference number of unity, and boasts a wide electrochemical stability window of greater than 4.5 V. Temperature-dependent ac impedance analysis reveals that the ionic conductivity of this material-and likely the other gels in the series-matches closely to a Vogel-Tamman-Fulcher temperature model.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1843007

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 16 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Polymer Electrolytes for Lithium-Ion Batteries Meyer, Wolfgang H. Advanced Materials, Vol. 10, Issue 6, p. 439-448 https://doi.org/10.1002/(SICI)1521-4095(199804)10:6<439::AID-ADMA439>3.0.CO;2-I	journal	April 1998
A Single‐Ion Conducting Borate Network Polymer as a Viable Quasi‐Solid Electrolyte for Lithium Metal Batteries Shin, Dong‐Myeong; Bachman, Jonathan E.; Taylor, Mercedes K. Advanced Materials, Vol. 32, Issue 10 https://doi.org/10.1002/adma.201905771	journal	January 2020
An Anionic Microporous Polymer Network Prepared by the Polymerization of Weakly Coordinating Anions Fischer, Sabrina; Schmidt, Johannes; Strauch, Peter Angewandte Chemie International Edition, Vol. 52, Issue 46 https://doi.org/10.1002/anie.201303045	journal	October 2013
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
Electrolytes for Lithium and Lithium-Ion Batteries Jow, T. Richard; Xu, Kang; Borodin, Oleg Modern Aspects of Electrochemistry https://doi.org/10.1007/978-1-4939-0302-3	book	January 2014
High performance PEO-based polymer electrolytes and their application in rechargeable lithium polymer batteries Sumathipala, H. H.; Hassoun, J.; Panero, S. Ionics, Vol. 13, Issue 5 https://doi.org/10.1007/s11581-007-0137-4	journal	August 2007
Conductivity and transference number measurements on polymer electrolytes Bruce, P. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90304-9	journal	September 1988
Polymer electrolytes from plasticized polyMOBs and their gel forms Xu, Wu; Angell, C. Austen Electrochimica Acta, Vol. 48, Issue 14-16 https://doi.org/10.1016/S0013-4686(03)00182-8	journal	June 2003
Onset of dendritic growth in lithium/polymer cells Rosso, M.; Gobron, T.; Brissot, C. Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00734-0	journal	July 2001
A single-ion polymer electrolyte based on boronate for lithium ion batteries Zhu, Y. S.; Gao, X. W.; Wang, X. J. Electrochemistry Communications, Vol. 22 https://doi.org/10.1016/j.elecom.2012.05.022	journal	August 2012
Synthesis, Characterization and Battery Performance of A Lithium Poly (4-vinylphenol) Phenolate Borate Composite Membrane Xu, Guodong; Zhang, Yunfeng; Rohan, Rupesh Electrochimica Acta, Vol. 139 https://doi.org/10.1016/j.electacta.2014.06.173	journal	September 2014
Ceramic and polymeric solid electrolytes for lithium-ion batteries Fergus, Jeffrey W. Journal of Power Sources, Vol. 195, Issue 15, p. 4554-4569 https://doi.org/10.1016/j.jpowsour.2010.01.076	journal	August 2010
Polyvinyl formal based single-ion conductor membranes as polymer electrolytes for lithium ion batteries Lian, Fang; Guan, Hong-yan; Wen, Yan Journal of Membrane Science, Vol. 469 https://doi.org/10.1016/j.memsci.2014.05.065	journal	November 2014
New gel polyelectrolytes for rechargeable lithium batteries Sun, X. Solid State Ionics, Vol. 175, Issue 1-4 https://doi.org/10.1016/j.ssi.2003.11.043	journal	November 2004
A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance Wang, Xuejiang; Liu, Zhihong; Kong, Qingshan Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.007	journal	September 2014
Synthesis and Lithium Ion Conduction of Polysiloxane Single-Ion Conductors Containing Novel Weak-Binding Borates Liang, Siwei; Choi, U. Hyeok; Liu, Wenjuan Chemistry of Materials, Vol. 24, Issue 12 https://doi.org/10.1021/cm3005387	journal	June 2012
Physical techniques for the study of solid electrolytes Linford, R. G.; Hackwood, S. Chemical Reviews, Vol. 81, Issue 4 https://doi.org/10.1021/cr00044a002	journal	August 1981
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
Crystalline Lithium Imidazolate Covalent Organic Frameworks with High Li-Ion Conductivity Hu, Yiming; Dunlap, Nathan; Wan, Shun Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.9b02448	journal	April 2019
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
Synthesis and Characterization of Network Single Ion Conductors Based on Comb-Branched Polyepoxide Ethers and Lithium Bis(allylmalonato)borate Sun, Xiao-Guang; Kerr, John B. Macromolecules, Vol. 39, Issue 1 https://doi.org/10.1021/ma0507701	journal	January 2006
Influence of Solvating Plasticizer on Ion Conduction of Polysiloxane Single-Ion Conductors Choi, U. Hyeok; Liang, Siwei; O’Reilly, Michael V. Macromolecules, Vol. 47, Issue 9 https://doi.org/10.1021/ma500146v	journal	April 2014
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid Nature Materials, Vol. 12, Issue 5 https://doi.org/10.1038/nmat3602	journal	March 2013
Synthesis and characterization of solid single ion conductors based on poly[lithium tetrakis(ethyleneboryl)borate] Cakmak, Güliz; Verhoeven, Aswin; Jansen, Martin J. Mater. Chem., Vol. 19, Issue 25 https://doi.org/10.1039/B811920A	journal	January 2009
Porous aromatic frameworks: Synthesis, structure and functions Ben, Teng; Qiu, Shilun CrystEngComm, Vol. 15, Issue 1 https://doi.org/10.1039/C2CE25409C	journal	January 2013
Covalent organic frameworks (COFs): from design to applications Ding, San-Yuan; Wang, Wei Chem. Soc. Rev., Vol. 42, Issue 2 https://doi.org/10.1039/C2CS35072F	journal	January 2013
Tetraarylborate polymer networks as single-ion conducting solid electrolytes Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin Chemical Science, Vol. 6, Issue 10 https://doi.org/10.1039/C5SC02052B	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
Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives Quartarone, Eliana; Mustarelli, Piercarlo Chemical Society Reviews, Vol. 40, Issue 5 https://doi.org/10.1039/c0cs00081g	journal	January 2011
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
Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview Agrawal, R. C.; Pandey, G. P. Journal of Physics D: Applied Physics, Vol. 41, Issue 22 https://doi.org/10.1088/0022-3727/41/22/223001	journal	October 2008
Electrochemical aspects of the generation of ramified metallic electrodeposits Chazalviel, J. -N. Physical Review A, Vol. 42, Issue 12 https://doi.org/10.1103/PhysRevA.42.7355	journal	December 1990
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
Polyelectrolyte Membranes Containing Lithium Malonato(difluoro)borate for Lithium-Ion Systems Driscoll, Peter F.; Yang, Li; Gervais, Matthieu 218th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.3557699	conference	January 2011
The Development and Future of Lithium Ion Batteries Blomgren, George E. Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0251701jes	journal	December 2016

Similar Records

Ionic conduction in 70-MeV C{sup 5+}-ion-irradiated poly(vinylidenefluoride- co-hexafluoropropylene)-based gel polymer electrolytes

Journal Article · 2005 · Journal of Applied Physics · OSTI ID:20714058

Saikia, D; Kumar, A; Singh, F; +2 more

Ionically conductive thin polymer films prepared by plasma polymerization; Preparation and characterization of ultrathin films having fixed sulfonic acid groups with only one mobile species

Journal Article · 1990 · Journal of the Electrochemical Society; (USA) · OSTI ID:6817792

Ogumi, Z; Uchimoto, Y; Takehara, Z; +1 more

Tuning Anion Composition and Mobility to Balance Ionic Conductivity and Cation Selectivity in Solid Polymer Electrolytes

Journal Article · 2026 · Macromolecules · OSTI ID:3363801

Yang, Mengying; Epps, III, Thomas H.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrical conductivity
electrolytes
lithium
materials
polymers

Title: Dependence of Linker Length and Composition on Ionic Conductivity and Lithium Deposition in Single-Ion Conducting Network Polymers

Citation Formats

References (36)

Similar Records

Related Subjects