DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes

Abstract

The ability to characterize bulk and interfacial transport properties of polymer electrolytes is critical to realizing their potential applications in electrochemical energy storage devices. In this paper, we leverage custom microfabricated interdigitated electrode array (IDEs) as a platform to probe ion transport properties of polymer electrolytes films through electrochemical impedance spectroscopy (EIS) measurements. Using poly(ethylene oxide) (PEO) blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as a model dry polymer electrolyte system, we investigate how geometric parameters of the IDEs influence the quality and analysis of EIS measurements. By focusing on films on the nanometer film thickness (ca. 50 nm), EIS measurements revealed diffusional processes near the electrode/polymer interface that may be difficult to observe with conventional thick films. Moreover, irreversible impedance spectra were observed at elevated temperatures when using IDEs with large electrode metal fractions. These irreversible processes were eliminated through passivation of the IDE with different oxides (SiO2, Al2O3, or TiO2). Ultimately, the ionic conductivity of PEO-LiTFSI electrolytes is confidently determined when appropriate IDE geometries and equivalent circuits are used. Lastly, our work demonstrates the use of IDEs and nanothin polymer electrolytes films as a versatile platform for rapid and efficient interrogation of both bulk and interfacial electrochemical properties.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1487126
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 16; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Films; Interdigitated electrodes; Polymer; Thin films

Citation Formats

Sharon, Daniel, Bennington, Peter, Liu, Claire, Kambe, Yu, Dong, Ban Xuan, Burnett, Veronica F., Dolejsi, Moshe, Grocke, Garrett, Patel, Shrayesh N., and Nealey, Paul F. Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes. United States: N. p., 2018. Web. doi:10.1149/2.0291816jes.
Sharon, Daniel, Bennington, Peter, Liu, Claire, Kambe, Yu, Dong, Ban Xuan, Burnett, Veronica F., Dolejsi, Moshe, Grocke, Garrett, Patel, Shrayesh N., & Nealey, Paul F. Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes. United States. https://doi.org/10.1149/2.0291816jes
Sharon, Daniel, Bennington, Peter, Liu, Claire, Kambe, Yu, Dong, Ban Xuan, Burnett, Veronica F., Dolejsi, Moshe, Grocke, Garrett, Patel, Shrayesh N., and Nealey, Paul F. Sat . "Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes". United States. https://doi.org/10.1149/2.0291816jes. https://www.osti.gov/servlets/purl/1487126.
@article{osti_1487126,
title = {Interrogation of Electrochemical Properties of Polymer Electrolyte Thin Films with Interdigitated Electrodes},
author = {Sharon, Daniel and Bennington, Peter and Liu, Claire and Kambe, Yu and Dong, Ban Xuan and Burnett, Veronica F. and Dolejsi, Moshe and Grocke, Garrett and Patel, Shrayesh N. and Nealey, Paul F.},
abstractNote = {The ability to characterize bulk and interfacial transport properties of polymer electrolytes is critical to realizing their potential applications in electrochemical energy storage devices. In this paper, we leverage custom microfabricated interdigitated electrode array (IDEs) as a platform to probe ion transport properties of polymer electrolytes films through electrochemical impedance spectroscopy (EIS) measurements. Using poly(ethylene oxide) (PEO) blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as a model dry polymer electrolyte system, we investigate how geometric parameters of the IDEs influence the quality and analysis of EIS measurements. By focusing on films on the nanometer film thickness (ca. 50 nm), EIS measurements revealed diffusional processes near the electrode/polymer interface that may be difficult to observe with conventional thick films. Moreover, irreversible impedance spectra were observed at elevated temperatures when using IDEs with large electrode metal fractions. These irreversible processes were eliminated through passivation of the IDE with different oxides (SiO2, Al2O3, or TiO2). Ultimately, the ionic conductivity of PEO-LiTFSI electrolytes is confidently determined when appropriate IDE geometries and equivalent circuits are used. Lastly, our work demonstrates the use of IDEs and nanothin polymer electrolytes films as a versatile platform for rapid and efficient interrogation of both bulk and interfacial electrochemical properties.},
doi = {10.1149/2.0291816jes},
journal = {Journal of the Electrochemical Society},
number = 16,
volume = 165,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Impedance spectroscopy investigation of electrophysical characteristics of the electrode-liquid crystal interface
journal, January 2015


A Precise, Reduced-Parameter Model of Thin Film Electrolyte Impedance
journal, January 2015

  • McNealy, Benjamin E.; Jiang, Jun; Hertz, Joshua L.
  • Journal of The Electrochemical Society, Vol. 162, Issue 6
  • DOI: 10.1149/2.0281506jes

Effect of Lithium-Ion Concentration on Morphology and Ion Transport in Single-Ion-Conducting Block Copolymer Electrolytes
journal, September 2015


The Compensation Effect in the Vogel–Tammann–Fulcher (VTF) Equation for Polymer-Based Electrolytes
journal, May 2017


Theoretical and experimental determination of cell constants of planar-interdigitated electrolyte conductivity sensors
journal, March 1995


Theoretical models for ac impedance of finite diffusion layers exhibiting low frequency dispersion
journal, October 1999

  • Bisquert, Juan; Garcia-Belmonte, Germà; Fabregat-Santiago, Francisco
  • Journal of Electroanalytical Chemistry, Vol. 475, Issue 2
  • DOI: 10.1016/S0022-0728(99)00346-0

Nanoscaled interdigitated electrode arrays for biochemical sensors
journal, June 1998


Proton Transport Property in Supported Nafion Nanothin Films by Electrochemical Impedance Spectroscopy
journal, January 2014

  • Paul, Devproshad K.; McCreery, Richard; Karan, Kunal
  • Journal of The Electrochemical Society, Vol. 161, Issue 14
  • DOI: 10.1149/2.0571414jes

Discontinuous Changes in Ionic Conductivity of a Block Copolymer Electrolyte through an Order–Disorder Transition
journal, January 2012

  • Teran, Alexander A.; Mullin, Scott A.; Hallinan, Daniel T.
  • ACS Macro Letters, Vol. 1, Issue 2
  • DOI: 10.1021/mz200183t

Characterization methodology for lead zirconate titanate thin films with interdigitated electrode structures
journal, May 2017

  • Nigon, R.; Raeder, T. M.; Muralt, P.
  • Journal of Applied Physics, Vol. 121, Issue 20
  • DOI: 10.1063/1.4983772

Capacitive sensing of droplets for microfluidic devices based on thermocapillary actuation
journal, January 2004

  • Chen, Jian Z.; Darhuber, Anton A.; Troian, Sandra M.
  • Lab on a Chip, Vol. 4, Issue 5
  • DOI: 10.1039/b315815b

Poly(ethylene oxide)-based electrolytes for lithium-ion batteries
journal, January 2015

  • Xue, Zhigang; He, Dan; Xie, Xiaolin
  • Journal of Materials Chemistry A, Vol. 3, Issue 38
  • DOI: 10.1039/C5TA03471J

AC frequency characteristics of coplanar impedance sensors as design parameters
journal, January 2005

  • Hong, Jongin; Yoon, Dae Sung; Kim, Sung Kwan
  • Lab on a Chip, Vol. 5, Issue 3
  • DOI: 10.1039/b410325d

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes
journal, January 2017

  • Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe
  • Journal of Materials Chemistry A, Vol. 5, Issue 11
  • DOI: 10.1039/C6TA10838E

Interdigital sensors and transducers
journal, May 2004


Impedance study of (PEO)10LiClO4–Al2O3 composite polymer electrolyte with blocking electrodes
journal, March 2001


Modeling of Interdigitated Electrodes and Supercapacitors with Porous Interdigitated Electrodes
journal, January 2017

  • Latimer, Katherine J.; Evans, James W.; Cowell, Martin A.
  • Journal of The Electrochemical Society, Vol. 164, Issue 4
  • DOI: 10.1149/2.0061706jes

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994

  • Lascaud, S.; Perrier, M.; Vallee, A.
  • Macromolecules, Vol. 27, Issue 25
  • DOI: 10.1021/ma00103a034

Polymer Electrolytes
journal, July 2013


CAD models for multilayered substrate interdigital capacitors
journal, June 1996

  • Gevorgian, S. S.; Martinsson, T.; Linner, P. L. J.
  • IEEE Transactions on Microwave Theory and Techniques, Vol. 44, Issue 6
  • DOI: 10.1109/22.506449

Proton-Conductivity Enhancement in Polymer Thin Films
journal, August 2017


Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films
journal, January 2016


Instability of Thin Polymer Films on Coated Substrates: Rupture, Dewetting, and Drop Formation
journal, March 1996

  • Sharma, Ashutosh; Reiter, Günter
  • Journal of Colloid and Interface Science, Vol. 178, Issue 2
  • DOI: 10.1006/jcis.1996.0133

Diffusion Impedance in a Thin-Layer Cell:  Experimental and Theoretical Study on a Large-Disk Electrode
journal, March 2008

  • Remita, E.; Boughrara, D.; Tribollet, B.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 12
  • DOI: 10.1021/jp710407a

Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes
journal, August 1995


Self-Assembly and Transport Limitations in Confined Nafion Films
journal, January 2013

  • Modestino, Miguel A.; Paul, Devproshad K.; Dishari, Shudipto
  • Macromolecules, Vol. 46, Issue 3, p. 867-873
  • DOI: 10.1021/ma301999a

Impedance of interface between PEO:LiTFSI polymer electrolyte and blocking electrodes
journal, October 2008


Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

  • Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900451e

Theory of the electrochemical impedance of macrohomogeneous porous electrodes
journal, December 1993


An Ambient Temperature Electrolyte with Superior Lithium Ion Conductivity based on a Self-Assembled Block Copolymer
journal, April 2018

  • Dörr, Tobias S.; Pelz, Alexander; Zhang, Peng
  • Chemistry - A European Journal, Vol. 24, Issue 32
  • DOI: 10.1002/chem.201801521

A Guide to Li-Ion Coin-Cell Electrode Making for Academic Researchers
journal, January 2011

  • Marks, Thomas; Trussler, Simon; Smith, A. J.
  • Journal of The Electrochemical Society, Vol. 158, Issue 1
  • DOI: 10.1149/1.3515072

Characterization of ion transport in thin films using electrochemical impedance spectroscopyI. Principles and theory
journal, September 2007


Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit
journal, February 2016


A Dielectric Model of Self-Assembled Monolayer Interfaces by Capacitive Spectroscopy
journal, June 2012

  • Góes, Márcio S.; Rahman, Habibur; Ryall, Joshua
  • Langmuir, Vol. 28, Issue 25
  • DOI: 10.1021/la301281y

Determination of Lithium-Ion Distributions in Nanostructured Block Polymer Electrolyte Thin Films by X-ray Photoelectron Spectroscopy Depth Profiling
journal, December 2014

  • Gilbert, Jonathan B.; Luo, Ming; Shelton, Cameron K.
  • ACS Nano, Vol. 9, Issue 1
  • DOI: 10.1021/nn505744r

An Ambient Temperature Electrolyte with Superior Lithium Ion Conductivity based on a Self-Assembled Block Copolymer
collection, January 2018

  • Dörr, Tobias S.; Pelz, Alexander; Zhang, Peng
  • Universität des Saarlandes
  • DOI: 10.22028/d291-28988

Works referencing / citing this record:

Nanothin film conductivity measurements reveal interfacial influence on ion transport in polymer electrolytes
journal, January 2019

  • Dong, Ban Xuan; Bennington, Peter; Kambe, Yu
  • Molecular Systems Design & Engineering, Vol. 4, Issue 3
  • DOI: 10.1039/c9me00011a