Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–CeZ+ as a Model System

Abstract

Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration,more » and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC)
OSTI Identifier:
1783118
Alternate Identifier(s):
OSTI ID: 1808837
Report Number(s):
LA-UR-20-23524
Journal ID: ISSN 2637-6105; ark:/13030/qt4vp9f41q
Grant/Contract Number:  
AC02-05CH11231; 89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Polymer Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 8; Journal ID: ISSN 2637-6105
Publisher:
ACS Publications
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ionomers; structure-property relationships; cation doping; concentrated solution theory; ion transport; Energy Sciences; Fuel Cell, Durability, cerium, Polymer electrolyte

Citation Formats

Baker, Andrew M., Crothers, Andrew R., Chintam, Kavitha, Luo, Xiaoyan, Weber, Adam Z., Borup, Rodney L., and Kusoglu, Ahmet. Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–CeZ+ as a Model System. United States: N. p., 2020. Web. doi:10.1021/acsapm.0c00633.
Copy to clipboard
Baker, Andrew M., Crothers, Andrew R., Chintam, Kavitha, Luo, Xiaoyan, Weber, Adam Z., Borup, Rodney L., & Kusoglu, Ahmet. Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–CeZ+ as a Model System. United States. https://doi.org/10.1021/acsapm.0c00633
Copy to clipboard
Baker, Andrew M., Crothers, Andrew R., Chintam, Kavitha, Luo, Xiaoyan, Weber, Adam Z., Borup, Rodney L., and Kusoglu, Ahmet. Thu . "Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–CeZ+ as a Model System". United States. https://doi.org/10.1021/acsapm.0c00633. https://www.osti.gov/servlets/purl/1783118.
Copy to clipboard
@article{osti_1783118,
title = {Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–CeZ+ as a Model System},
author = {Baker, Andrew M. and Crothers, Andrew R. and Chintam, Kavitha and Luo, Xiaoyan and Weber, Adam Z. and Borup, Rodney L. and Kusoglu, Ahmet},
abstractNote = {Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration, and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.},
doi = {10.1021/acsapm.0c00633},
journal = {ACS Applied Polymer Materials},
number = 8,
volume = 2,
place = {United States},
year = {Thu Jun 25 00:00:00 EDT 2020},
month = {Thu Jun 25 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsapm.0c00633
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
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:

Effect of Cerium, Cobalt and Nickel Contaminants on the Oxygen Reduction Reaction at Platinum Electrodes
journal, August 2017

  • Dumont, Joseph H.; Baker, Andrew M.; Maurya, Sandip
  • ECS Transactions, Vol. 80, Issue 8
  • DOI: 10.1149/08008.0861ecst

Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation
journal, January 2020

  • Crothers, Andrew R.; Darling, Robert M.; Kusoglu, Ahmet
  • Journal of The Electrochemical Society, Vol. 167, Issue 1
  • DOI: 10.1149/1945-7111/ab6724

Effect of Relative Humidity on Membrane Degradation Rate and Mechanism in PEM Fuel Cells
conference, January 2007

  • Xu, Hui; Boroup, Rodney; Brosha, Eric
  • 211th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2811696

Degradation reduction of polymer electrolyte membranes using CeO2 as a free-radical scavenger in catalyst layer
journal, October 2013

Modeling the steady-state effects of cationic contamination on polymer electrolyte membranes
journal, February 2009

Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes
journal, December 2017

  • Crothers, Andrew R.; Radke, Clayton J.; Weber, Adam Z.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 51
  • DOI: 10.1021/acs.jpcc.7b07360

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability
journal, January 2017

  • Baker, Andrew M.; Williams, Stefan T. D.; Mukundan, Rangachary
  • Journal of Materials Chemistry A, Vol. 5, Issue 29
  • DOI: 10.1039/C7TA03452K

Local Degradation at Membrane Defects in Polymer Electrolyte Fuel Cells
journal, January 2013

  • Kreitmeier, Stefan; Lerch, Philippe; Wokaun, Alexander
  • Journal of The Electrochemical Society, Vol. 160, Issue 4
  • DOI: 10.1149/1.023306jes

Determination of Ce 3+ and Co 2+ Diffusion Coefficients in NR211 Membrane
journal, July 2018

Cerium Migration during PEM Fuel Cell Accelerated Stress Testing
journal, January 2016

  • Baker, Andrew M.; Mukundan, Rangachary; Spernjak, Dusan
  • Journal of The Electrochemical Society, Vol. 163, Issue 9
  • DOI: 10.1149/2.0181609jes

The Chemistry of Fuel Cell Membrane Chemical Degradation
conference, January 2008

Development of Operando Confocal Microprobe X-ray Fluorescence Techniques to Measure Cation Transport in PEM Fuel Cells
journal, July 2019

  • Baker, Andrew M.; Cai, Yun; Ziegelbauer, Joseph M.
  • ECS Transactions, Vol. 92, Issue 8
  • DOI: 10.1149/09208.0107ecst

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation
journal, January 2017

  • Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary
  • Journal of The Electrochemical Society, Vol. 164, Issue 12
  • DOI: 10.1149/2.1221712jes

Mechanism of Perfluorsulfonic Acid Membrane Chemical Degradation Under Low RH Conditions
journal, March 2013

Fuel Cell Perfluorinated Sulfonic Acid Membrane Degradation Correlating Accelerated Stress Testing and Lifetime
journal, September 2012

  • Rodgers, Marianne P.; Bonville, Leonard J.; Kunz, H. Russell
  • Chemical Reviews, Vol. 112, Issue 11
  • DOI: 10.1021/cr200424d

A Critical Review of Modeling Transport Phenomena in Polymer-Electrolyte Fuel Cells
journal, January 2014

  • Weber, Adam Z.; Borup, Rodney L.; Darling, Robert M.
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0751412jes

In-Situ Modeling of Chemical Membrane Degradation and Mitigation in Ceria-Supported Fuel Cells
journal, January 2017

  • Wong, Ka Hung; Kjeang, Erik
  • Journal of The Electrochemical Society, Vol. 164, Issue 12
  • DOI: 10.1149/2.1201712jes

Water Transport Behavior in Nafion 117 Membranes
journal, January 1995

  • Xie, Gang
  • Journal of The Electrochemical Society, Vol. 142, Issue 9
  • DOI: 10.1149/1.2048686

Degradation Mitigation in Polymer Electrolyte Membranes Using Cerium Oxide as a Regenerative Free-Radical Scavenger
journal, January 2008

  • Trogadas, Panagiotis; Parrondo, Javier; Ramani, Vijay
  • Electrochemical and Solid-State Letters, Vol. 11, Issue 7
  • DOI: 10.1149/1.2916443

Advanced Redox-Flow Batteries: A Perspective
journal, September 2015

  • Perry, Mike L.; Weber, Adam Z.
  • Journal of The Electrochemical Society, Vol. 163, Issue 1
  • DOI: 10.1149/2.0101601jes

Mitigation of Perfluorosulfonic Acid Membrane Chemical Degradation Using Cerium and Manganese Ions
conference, January 2008

  • Coms, Frank D.; Liu, Han; Owejan, Jeanette E.
  • 214th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2982015

The degradation mitigation effect of cerium oxide in polymer electrolyte membranes in extended fuel cell durability tests
journal, March 2013

Unraveling the local energetics of transport in a polymer ion conductor
journal, January 2013

  • Lingwood, Mark D.; Zhang, Zhiyang; Kidd, Bryce E.
  • Chemical Communications, Vol. 49, Issue 39
  • DOI: 10.1039/c2cc37173a

Impact of CeOx Additives on Cathode Catalyst Layer Poisoning
journal, August 2013

Full Factorial Experiment to Determine and Predict Impact of Cerium Amount on Fuel Cell Performance
journal, August 2017

  • Redmond, Erin L.; Wriston, Shirley; Szarka, John L.
  • ECS Transactions, Vol. 80, Issue 8
  • DOI: 10.1149/08008.0633ecst

Progress Toward Accurate Through-Plane Ion Transport Resistance Measurement of Thin Solid Electrolytes
journal, January 2010

  • Cooper, Kevin R.
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3481561

A Mechanistic Study of Perfluorosulfonic Acid Membrane Water Permeance Degradation in Air
journal, January 2018

  • Coms, Frank D.; Fuller, Timothy J.; Schaffer, Corey P.
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0141806jes

Cerium Migration through Hydrogen Fuel Cells during Accelerated Stress Testing
journal, January 2014

  • Stewart, S. M.; Spernjak, D.; Borup, R.
  • ECS Electrochemistry Letters, Vol. 3, Issue 4
  • DOI: 10.1149/2.008404eel

Chemical and Morphological Origins of Improved Ion Conductivity in Perfluoro Ionene Chain Extended Ionomers
journal, August 2019

  • Su, Gregory M.; Cordova, Isvar A.; Yandrasits, Michael A.
  • Journal of the American Chemical Society, Vol. 141, Issue 34
  • DOI: 10.1021/jacs.9b05322

Membrane Accelerated Stress Test Development for Polymer Electrolyte Fuel Cell Durability Validated Using Field and Drive Cycle Testing
journal, January 2018

  • Mukundan, Rangachary; Baker, Andrew M.; Kusoglu, Ahmet
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0101806jes

Ion and Water Transport Characteristics in Membranes for Polymer Electrolyte Fuel Cells Containing H[sup +] and Ca[sup 2+] Cations
journal, January 1997

  • Okada, Tatsuhiro
  • Journal of The Electrochemical Society, Vol. 144, Issue 8
  • DOI: 10.1149/1.1837890

The ion and water transport properties of K+ and Na+ form perfluorosulfonic acid polymer
journal, August 2018

New Insights into Perfluorinated Sulfonic-Acid Ionomers
journal, January 2017

Estimation of Cation Contamination Level in Polymer Electrolyte Membrane Fuel Cells by Electrochemical Impedance Spectroscopy
journal, June 2018

  • Shibata, Masao; Kitano, Naoki; Shinohara, Akihiro
  • ECS Transactions, Vol. 85, Issue 13
  • DOI: 10.1149/08513.0905ecst

Modeling Coupled Durability and Performance in Polymer-Electrolyte Fuel Cells: Membrane Effects
journal, January 2019

  • Ehlinger, Victoria M.; Kusoglu, Ahmet; Weber, Adam Z.
  • Journal of The Electrochemical Society, Vol. 166, Issue 7
  • DOI: 10.1149/2.0281907jes

Membrane degradation during combined chemical and mechanical accelerated stress testing of polymer electrolyte fuel cells
journal, July 2014

Proton Solvation and Transport in Aqueous and Biomolecular Systems:  Insights from Computer Simulations
journal, May 2007

  • Swanson, Jessica M. J.; Maupin, C. Mark; Chen, Hanning
  • The Journal of Physical Chemistry B, Vol. 111, Issue 17
  • DOI: 10.1021/jp070104x

Structure/property relationship of Nafion XL composite membranes
journal, October 2016

Mechanisms of Ion and Water Transport in Perfluorosulfonated Ionomer Membranes for Fuel Cells
journal, October 2004

  • Saito, Morihiro; Arimura, Naoko; Hayamizu, Kikuko
  • The Journal of Physical Chemistry B, Vol. 108, Issue 41
  • DOI: 10.1021/jp0482565

Study of Self-Diffusion of Monovalent and Divalent Cations in Nafion-117 Ion-Exchange Membrane
journal, September 2001

  • Goswami, A.; Acharya, Anjali; Pandey, A. K.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 38
  • DOI: 10.1021/jp010529y

Water orientation and ion solvation effects during multicomponent salt partitioning in a Nafion cation exchange membrane
journal, January 1994

Computational study of the cerium(III) ion in aqueous environment
journal, June 2012

Development of a Method for Clarifying the Perfluorosulfonated Membrane Degradation Mechanism in a Fuel Cell Environment
journal, January 2008

  • Hommura, Satoru; Kawahara, Kengo; Shimohira, Tetsuji
  • Journal of The Electrochemical Society, Vol. 155, Issue 1
  • DOI: 10.1149/1.2800171

Mathematical Modeling of a Cation-Exchange Membrane Containing Two Cations
journal, January 2008

  • Delacourt, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 155, Issue 11, p. B1210-B1217
  • DOI: 10.1149/1.2977960

Mathematical Modelling of Cation Contamination in a Proton-exchange Membrane
journal, December 2008

The Effect of Impurity Cations on the Transport Characteristics of Perfluorosulfonated Ionomer Membranes
journal, April 1999

  • Okada, Tatsuhiro; Ayato, Yuusuke; Yuasa, Makoto
  • The Journal of Physical Chemistry B, Vol. 103, Issue 17
  • DOI: 10.1021/jp983762d

Structure-Transport Relationship of Perfluorosulfonic-Acid Membranes in Different Cationic Forms
journal, December 2016

Kinetic Simulation of the Chemical Stabilization Mechanism in Fuel Cell Membranes Using Cerium and Manganese Redox Couples
journal, January 2011

  • Gubler, Lorenz; Koppenol, Willem H.
  • Journal of The Electrochemical Society, Vol. 159, Issue 2
  • DOI: 10.1149/2.075202jes

A Molecular Dynamics Study of the Effects of V 2+ and V 3+ on the Local Structure of Hydrated Nafion
journal, June 2015

  • Cui, Shengting; Paddison, Stephen J.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 23
  • DOI: 10.1021/acs.jpcc.5b02876

Diffusion and Interfacial Transport of Water in Nafion
journal, March 2011

  • Zhao, Qiao; Majsztrik, Paul; Benziger, Jay
  • The Journal of Physical Chemistry B, Vol. 115, Issue 12
  • DOI: 10.1021/jp1112125

Multicomponent space-charge transport model for ion-exchange membranes
journal, June 2000

In-situ diagnostics and degradation mapping of a mixed-mode accelerated stress test for proton exchange membranes
journal, January 2015

Simulation of Performance Tradeoffs in Ceria Supported Polymer Electrolyte Fuel Cells
journal, January 2019

  • Wong, Ka Hung; Kjeang, Erik
  • Journal of The Electrochemical Society, Vol. 166, Issue 2
  • DOI: 10.1149/2.0771902jes

Ce Cation Migration and Diffusivity in Perfluorosulfonic Acid Fuel Cell Membranes
journal, July 2019

  • Baker, Andrew M.; Komini Babu, Siddharth; Chintam, Kavitha
  • ECS Transactions, Vol. 92, Issue 8
  • DOI: 10.1149/09208.0429ecst

Role of Mechanical Factors in Controlling the Structure–Function Relationship of PFSA Ionomers
journal, September 2012

  • Kusoglu, Ahmet; Savagatrup, Suchol; Clark, Kyle T.
  • Macromolecules, Vol. 45, Issue 18
  • DOI: 10.1021/ma301419s

Divalent/monovalent cation uptake selectivity in a Nafion cation-exchange membrane: Experimental and modeling studies
journal, December 1997

Electrode Edge Cobalt Cation Migration in an Operating Fuel Cell: An In Situ Micro-X-ray Fluorescence Study
journal, January 2018

  • Cai, Yun; Ziegelbauer, Joseph M.; Baker, Andrew M.
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0201806jes

Transport and equilibrium properties of Nafion® membranes with H+ and Na+ ions
journal, January 1998

  • Okada, Tatsuhiro; Møller-Holst, Steffen; Gorseth, Oddvar
  • Journal of Electroanalytical Chemistry, Vol. 442, Issue 1-2
  • DOI: 10.1016/S0022-0728(97)00499-3

Effect of cations (Na+, Ca2+, Fe3+) on the conductivity of a Nafion membrane
journal, November 2010

Ion and water transport characteristics of Nafion membranes as electrolytes
journal, August 1998

Accelerated Stress Testing of Fuel Cell Membranes Subjected to Combined Mechanical/Chemical Stressors and Cerium Migration
journal, January 2018

  • Lai, Yeh-Hung; Rahmoeller, Kenneth M.; Hurst, James H.
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0241806jes

Radical (HO●, H● and HOO●) Formation and Ionomer Degradation in Polymer Electrolyte Fuel Cells
journal, January 2011

  • Gubler, Lorenz; Dockheer, Sindy M.; Koppenol, Willem H.
  • Journal of The Electrochemical Society, Vol. 158, Issue 7
  • DOI: 10.1149/1.3581040

Migration of Ce and Mn Ions in PEMFC and Its Impact on PFSA Membrane Degradation
journal, January 2018

  • Zatoń, Marta; Prélot, Benedicte; Donzel, Nicolas
  • Journal of The Electrochemical Society, Vol. 165, Issue 6
  • DOI: 10.1149/2.0311806jes
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: