A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes
Abstract
Polymer–ceramic composite electrolytes are promising for the application of all-solid-state lithium-ion batteries with high energy density and improved safety. In this work, we employ temperature-dependent 7Li and 19F NMR to examine the chemical environment and the dynamics of Li+ cation and triflate anion in poly(ethylene oxide) (PEO)–lithium triflate (LiTf) polymer electrolyte and a composite electrolyte containing 55 vol % doped lithium aluminum titanium phosphate (LICGC). The line shape analysis and spin–lattice relaxation (T1) measurements suggest both the Li+ cations and the Tf– anions reside in two distinct environment: a mobile environment and an immobile environment. In the semicrystalline state, a large ratio (>70%) of immobile Li+ and Tf– is observed. In the melt state, the ratio of mobile cations and anions significantly increases. With the presence of LICGC ceramic, an increased ratio of immobile Li+ and Tf– and reduced mobility of the mobile components are observed, indicating that the ceramic negatively impacts the transport of both the cations and the anions. NMR characterizations are corroborated by conductivity results, which reveal that the intrinsic ionic conductivity of the polymer phase of the composite electrolyte was only 0.15 of the ceramic-free polymer electrolyte at room temperature. These results shed light on themore »
- Authors:
-
[4]
- Beihang Univ., Beijing (China)
- Hunter College of the City Univ. of New York, NY (United States)
- 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)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1761677
- Grant/Contract Number:
- AC05-00OR22725; N00014-18-1-2720; N00014-16-1-2579
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Polymer Materials
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2637-6105
- Publisher:
- ACS Publications
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; solid state NMR; polymer electrolyte; composite electrolyte; ionic conductivity; lithium battery
Citation Formats
Peng, Jing, Xiao, Ye, Clarkson, David A., Greenbaum, Steven G., Zawodzinski, Thomas A., and Chen, X. Chelsea. A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes. United States: N. p., 2020.
Web. doi:10.1021/acsapm.9b01068.
Peng, Jing, Xiao, Ye, Clarkson, David A., Greenbaum, Steven G., Zawodzinski, Thomas A., & Chen, X. Chelsea. A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes. United States. https://doi.org/10.1021/acsapm.9b01068
Peng, Jing, Xiao, Ye, Clarkson, David A., Greenbaum, Steven G., Zawodzinski, Thomas A., and Chen, X. Chelsea. Mon .
"A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes". United States. https://doi.org/10.1021/acsapm.9b01068. https://www.osti.gov/servlets/purl/1761677.
@article{osti_1761677,
title = {A Nuclear Magnetic Resonance Study of Cation and Anion Dynamics in Polymer–Ceramic Composite Solid Electrolytes},
author = {Peng, Jing and Xiao, Ye and Clarkson, David A. and Greenbaum, Steven G. and Zawodzinski, Thomas A. and Chen, X. Chelsea},
abstractNote = {Polymer–ceramic composite electrolytes are promising for the application of all-solid-state lithium-ion batteries with high energy density and improved safety. In this work, we employ temperature-dependent 7Li and 19F NMR to examine the chemical environment and the dynamics of Li+ cation and triflate anion in poly(ethylene oxide) (PEO)–lithium triflate (LiTf) polymer electrolyte and a composite electrolyte containing 55 vol % doped lithium aluminum titanium phosphate (LICGC). The line shape analysis and spin–lattice relaxation (T1) measurements suggest both the Li+ cations and the Tf– anions reside in two distinct environment: a mobile environment and an immobile environment. In the semicrystalline state, a large ratio (>70%) of immobile Li+ and Tf– is observed. In the melt state, the ratio of mobile cations and anions significantly increases. With the presence of LICGC ceramic, an increased ratio of immobile Li+ and Tf– and reduced mobility of the mobile components are observed, indicating that the ceramic negatively impacts the transport of both the cations and the anions. NMR characterizations are corroborated by conductivity results, which reveal that the intrinsic ionic conductivity of the polymer phase of the composite electrolyte was only 0.15 of the ceramic-free polymer electrolyte at room temperature. These results shed light on the challenges inherent to composite electrolytes with the goal of achieving both enhanced Li+ transference number and ionic conductivity.},
doi = {10.1021/acsapm.9b01068},
journal = {ACS Applied Polymer Materials},
number = 3,
volume = 2,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2020},
month = {Mon Mar 02 00:00:00 EST 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Complexes of alkali metal ions with poly(ethylene oxide)
journal, November 1973
- Fenton, D. E.; Parker, J. M.; Wright, P. V.
- Polymer, Vol. 14, Issue 11
The history of polymer electrolytes
journal, August 1994
- Armand, M.
- Solid State Ionics, Vol. 69, Issue 3-4
Hot-pressed, solvent-free, nanocomposite, PEO-based electrolyte membranes
journal, October 2003
- Appetecchi, G. B.; Hassoun, J.; Scrosati, B.
- Journal of Power Sources, Vol. 124, Issue 1
Toward high lithium conduction in solid polymer and polymer–ceramic batteries
journal, June 2018
- Commarieu, Basile; Paolella, Andrea; Daigle, Jean-Christophe
- Current Opinion in Electrochemistry, Vol. 9
Building Better Batteries in the Solid State: A Review
journal, November 2019
- Mauger, Alain; Julien, Christian M.; Paolella, Andrea
- Materials, Vol. 12, Issue 23, p. 3892
Structural and ionic conductivity of PEO blend PEG solid polymer electrolyte
journal, January 2006
- Jaipal Reddy, M.; Siva Kumar, J.; Subba Rao, U. V.
- Solid State Ionics, Vol. 177, Issue 3-4
Microscopic investigation of ionic conductivity in alkali metal salts-poly(ethylene oxide) adducts
journal, September 1983
- Berthier, C.; Gorecki, W.; Minier, M.
- Solid State Ionics, Vol. 11, Issue 1
Effects of Al2O3 nanofiller and EC plasticizer on the ionic conductivity enhancement of solid PEO–LiCF3SO3 solid polymer electrolyte
journal, August 2011
- Johan, Mohd Rafie; Shy, Oon Hooi; Ibrahim, Suriani
- Solid State Ionics, Vol. 196, Issue 1
Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO 2 nanoparticles
journal, January 2014
- Tominaga, Yoichi; Yamazaki, Kenta
- Chem. Commun., Vol. 50, Issue 34
Influence of Fe 2 O 3 Nanofiller Shape on the Conductivity and Thermal Properties of Solid Polymer Electrolytes: Nanorods versus Nanospheres
journal, September 2012
- Do, Nhu Suong T.; Schaetzl, Dean M.; Dey, Barnali
- The Journal of Physical Chemistry C, Vol. 116, Issue 40
Influence of MOF ligands on the electrochemical and interfacial properties of PEO-based electrolytes for all-solid- state lithium batteries
journal, October 2019
- Mathew, Deepa Elizabeth; Gopi, Sivalingam; Kathiresan, Murugavel
- Electrochimica Acta, Vol. 319
A ceramic/polymer composite solid electrolyte for sodium batteries
journal, January 2016
- Zhang, Zhizhen; Zhang, Qiangqiang; Ren, Cheng
- Journal of Materials Chemistry A, Vol. 4, Issue 41
All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes
journal, August 2015
- Lago, Nerea; Garcia-Calvo, Oihane; Lopez del Amo, Juan Miguel
- ChemSusChem, Vol. 8, Issue 18
Enhanced Lithium Battery with Polyethylene Oxide-Based Electrolyte Containing Silane-Al 2 O 3 Ceramic Filler
journal, June 2013
- Zewde, Berhanu W.; Admassie, Shimelis; Zimmermann, Jutta
- ChemSusChem, Vol. 6, Issue 8
PEO based composite solid electrolyte containing nasicon
journal, September 1988
- Pcharski, J.
- Solid State Ionics, Vol. 28-30
High Lithium-Ion-Conducting NASICON-Type Li1+xAlxGeyTi2−x−y(PO4)3 Solid Electrolyte
journal, April 2016
- Xuefu, Shang; Nemori, Hiroyoshi; Mitsuoka, Shigehi
- Frontiers in Energy Research, Vol. 4
Flexible Composite Solid Electrolyte Facilitating Highly Stable “Soft Contacting” Li-Electrolyte Interface for Solid State Lithium-Ion Batteries
journal, September 2017
- Yang, Luyi; Wang, Zijian; Feng, Yancong
- Advanced Energy Materials, Vol. 7, Issue 22
A new composite solid electrolyte PEO/Li10GeP2S12/SN for all-solid-state lithium battery
journal, August 2016
- Chen, Bo; Huang, Zhen; Chen, Xiaotian
- Electrochimica Acta, Vol. 210
Lithium Ion Pathway within Li 7 La 3 Zr 2 O 12 -Polyethylene Oxide Composite Electrolytes
journal, September 2016
- Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan
- Angewandte Chemie, Vol. 128, Issue 40
PEO/garnet composite electrolytes for solid-state lithium batteries: From “ceramic-in-polymer” to “polymer-in-ceramic”
journal, April 2018
- Chen, Long; Li, Yutao; Li, Shuai-Peng
- Nano Energy, Vol. 46
Advanced, high-performance composite polymer electrolytes for lithium batteries
journal, October 2006
- Croce, F.; Sacchetti, S.; Scrosati, B.
- Journal of Power Sources, Vol. 161, Issue 1
A promising PEO/LAGP hybrid electrolyte prepared by a simple method for all-solid-state lithium batteries
journal, November 2016
- Zhao, Yanran; Huang, Zhen; Chen, Shaojie
- Solid State Ionics, Vol. 295
Ionic Conductivity Enhancement of Polymer Electrolytes with Ceramic Nanowire Fillers
journal, March 2015
- Liu, Wei; Liu, Nian; Sun, Jie
- Nano Letters, Vol. 15, Issue 4, p. 2740-2745
Synergistic Coupling between Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 and Poly(vinylidene fluoride) Induces High Ionic Conductivity, Mechanical Strength, and Thermal Stability of Solid Composite Electrolytes
journal, September 2017
- Zhang, Xue; Liu, Ting; Zhang, Shuofeng
- Journal of the American Chemical Society, Vol. 139, Issue 39
Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes
journal, May 2001
- Croce, F.; Persi, L.; Scrosati, B.
- Electrochimica Acta, Vol. 46, Issue 16
Analysis of composite electrolytes with sintered reinforcement structure for energy storage applications
journal, November 2013
- Kalnaus, Sergiy; Tenhaeff, Wyatt E.; Sakamoto, Jeffrey
- Journal of Power Sources, Vol. 241
Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings
journal, June 2018
- Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua
- Journal of Power Sources, Vol. 390
Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface
journal, April 2019
- Chen, X. Chelsea; Liu, Xiaoming; Samuthira Pandian, Amaresh
- ACS Energy Letters, Vol. 4, Issue 5
Electrochemical and solid state NMR characterization of composite PEO-based polymer electrolytes
journal, June 2003
- Cheung, I. W.; Chin, K. B.; Greene, E. R.
- Electrochimica Acta, Vol. 48, Issue 14-16
A multinuclear NMR study of ion transport in P(EO)nLiBETI complexes
journal, March 2005
- Suarez, S.; Jayakody, J.; Abbrent, S.
- Solid State Ionics, Vol. 176, Issue 11-12
A three-dimensional interconnected polymer/ceramic composite as a thin film solid electrolyte
journal, April 2020
- Palmer, Max J.; Kalnaus, Sergiy; Dixit, Marm B.
- Energy Storage Materials, Vol. 26
Phase Diagrams and Conductivity Characterization of Some PEO-LiX Electrolytes
journal, January 1986
- Robitaille, C. D.
- Journal of The Electrochemical Society, Vol. 133, Issue 2
The effect of type of the inorganic filler and dopant salt concentration on the PEO–LiClO4 based composite electrolyte–lithium electrode interfacial resistivity
journal, September 2006
- Bac, A.; Ciosek, M.; Bukat, M.
- Journal of Power Sources, Vol. 159, Issue 1
Nanocomposite polymer electrolytes for lithium batteries
journal, July 1998
- Croce, F.; Appetecchi, G. B.; Persi, L.
- Nature, Vol. 394, Issue 6692
Electrochemical and spectroscopic study of the transport properties of composite polymer electrolytes
journal, November 1992
- Croce, F.; Scrosati, B.; Mariotto, G.
- Chemistry of Materials, Vol. 4, Issue 6
Relation between glass transition and melting of PEO–salt complexes
journal, January 2000
- Kim, Y. W.; Lee, W.; Choi, B. K.
- Electrochimica Acta, Vol. 45, Issue 8-9
Solution-Based Synthesis and Characterization of Lithium-Ion Conducting Phosphate Ceramics for Lithium Metal Batteries
journal, December 2011
- Key, Baris; Schroeder, David J.; Ingram, Brian J.
- Chemistry of Materials, Vol. 24, Issue 2
Lithium ion mobility in poly(vinyl alcohol) based polymer electrolytes as determined by 7Li NMR spectroscopy
journal, April 1998
- Every, H. A.; Zhou, F.; Forsyth, M.
- Electrochimica Acta, Vol. 43, Issue 10-11
A 7 Li NMR study of the superconducting spinel Li 1+x Ti 2-x O 4
journal, October 1994
- Dalton, M.; Tunstall, D. P.; Todd, J.
- Journal of Physics: Condensed Matter, Vol. 6, Issue 42
A 7 Li nuclear magnetic resonance study of LiCF 3 SO 3 complexed in poly(propylene‐glycol)
journal, February 1991
- Chung, S. H.; Jeffrey, K. R.; Stevens, J. R.
- The Journal of Chemical Physics, Vol. 94, Issue 3
Lithium-7 NMR and ionic conductivity studies of gel electrolytes based on poly(methylmethacrylate)
journal, October 1995
- Stallworth, P. E.; Greenbaum, S. G.; Croce, F.
- Electrochimica Acta, Vol. 40, Issue 13-14
Electrical, thermal and NMR investigation of composite solid electrolytes based on PEO, LiI and high surface area inorganic oxides
journal, April 1998
- Dai, Y.; Wang, Y.; Greenbaum, S. G.
- Electrochimica Acta, Vol. 43, Issue 10-11
Solid state NMR characterization of lithium conducting ceramics
journal, July 1996
- Nairn, K.
- Solid State Ionics, Vol. 86-88
Thermal analysis and NMR study of a poly(ethylene oxide) complex electrolyte : PEO(LiCF3SO3)x
journal, January 1984
- Minier, M.; Berthier, C.; Gorecki, W.
- Journal de Physique, Vol. 45, Issue 4
Study of the molecular motions of polyethylene by line-shape analysis of broad-line proton NMR spectra
journal, September 1978
- Bergmann, Klaus
- Journal of Polymer Science: Polymer Physics Edition, Vol. 16, Issue 9
Mathematical separation procedure of broadline proton NMR spectra of crystalline polymers into components
journal, March 1979
- Unterforsthuber, Klaus; Bergmann, Klaus
- Journal of Magnetic Resonance (1969), Vol. 33, Issue 3
Ionic conductivity and 7Li NMR Study of Poly(ethylene glycol) complexed with lithium salts
journal, January 1992
- Panero, S.; Scrosati, B.; Greenbaum, S. G.
- Electrochimica Acta, Vol. 37, Issue 9
Nuclear quadrupole resonance spectroscopy. General principles
journal, January 1971
- Smith, J. A. S.
- Journal of Chemical Education, Vol. 48, Issue 1
New Insights into the Compositional Dependence of Li-Ion Transport in Polymer–Ceramic Composite Electrolytes
journal, January 2018
- Zheng, Jin; Hu, Yan-Yan
- ACS Applied Materials & Interfaces, Vol. 10, Issue 4
Solid-to-liquid transition of polycarbonate solid electrolytes in Li-metal batteries
journal, October 2019
- Commarieu, Basile; Paolella, Andrea; Collin-Martin, Steve
- Journal of Power Sources, Vol. 436
Properties of the Interphase Formed between Argyrodite-Type Li 6 PS 5 Cl and Polymer-Based PEO 10 :LiTFSI
journal, October 2019
- Simon, Fabian J.; Hanauer, Matthias; Henss, Anja
- ACS Applied Materials & Interfaces, Vol. 11, Issue 45
19 F and 13 C NMR Signal Assignment and Analysis in a Perfluorinated Ionomer (Nafion) by Two-Dimensional Solid-State NMR
journal, August 2004
- Chen, Q.; Schmidt-Rohr, K.
- Macromolecules, Vol. 37, Issue 16
Infrared Spectroscopic Study of the Phases and Phase Transitions in Poly(ethylene oxide) and Poly(ethylene oxide)-Lithium Trifluoromethanesulfonate Complexes
journal, July 1995
- Dissanayake, M. A. K. L.; Frech, Roger
- Macromolecules, Vol. 28, Issue 15
A 7Li and 19F NMR relaxation study of LiCF3SO3 in plasticised solid polyether electrolytes
journal, December 1995
- Ali, F.; Forsyth, M.; Garcia, M. C.
- Solid State Nuclear Magnetic Resonance, Vol. 5, Issue 3
Heterogeneous 7Li NMR relaxation in nanocrystalline Li2O:B2O3 composites
journal, September 2002
- Indris, Sylvio; Heitjans, Paul
- Journal of Non-Crystalline Solids, Vol. 307-310
Evaluation of ion-transport in composite polymer-in-ceramic electrolytes. Case study of active and inert ceramics
journal, May 2019
- Menkin, S.; Lifshitz, M.; Haimovich, A.
- Electrochimica Acta, Vol. 304