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

Baker, Andrew M.; Crothers, Andrew R.; Chintam, Kavitha; Luo, Xiaoyan; Weber, Adam Z.; Borup, Rodney L.; Kusoglu, Ahmet

doi:10.1021/acsapm.0c00633

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

Journal Article · Thu Jun 25 00:00:00 EDT 2020 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.0c00633· OSTI ID:1783118

^[1];

^[2]; Chintam, Kavitha ^[1]; Luo, Xiaoyan ^[2];

^[2];

^[1];

^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; 89233218CNA000001

OSTI ID:: 1783118

Alternate ID(s):: OSTI ID: 1808837

Report Number(s):: LA-UR-20-23524; ark:/13030/qt4vp9f41q

Journal Information:: ACS Applied Polymer Materials, Vol. 2, Issue 8; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Effect of Cerium, Cobalt and Nickel Contaminants on the Oxygen Reduction Reaction at Platinum Electrodes Dumont, Joseph H.; Baker, Andrew M.; Maurya, Sandip ECS Transactions, Vol. 80, Issue 8 https://doi.org/10.1149/08008.0861ecst	journal	August 2017
Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation Crothers, Andrew R.; Darling, Robert M.; Kusoglu, Ahmet Journal of The Electrochemical Society, Vol. 167, Issue 1 https://doi.org/10.1149/1945-7111/ab6724	journal	January 2020
Effect of Relative Humidity on Membrane Degradation Rate and Mechanism in PEM Fuel Cells Xu, Hui; Boroup, Rodney; Brosha, Eric 211th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2811696	conference	January 2007
Degradation reduction of polymer electrolyte membranes using CeO2 as a free-radical scavenger in catalyst layer Wang, Liang; Advani, Suresh G.; Prasad, Ajay K. Electrochimica Acta, Vol. 109 https://doi.org/10.1016/j.electacta.2013.07.189	journal	October 2013
Modeling the steady-state effects of cationic contamination on polymer electrolyte membranes Kienitz, B. L.; Baskaran, H.; Zawodzinski, T. A. Electrochimica Acta, Vol. 54, Issue 6 https://doi.org/10.1016/j.electacta.2008.09.058	journal	February 2009
Impact of Nano- and Mesoscales on Macroscopic Cation Conductivity in Perfluorinated-Sulfonic-Acid Membranes Crothers, Andrew R.; Radke, Clayton J.; Weber, Adam Z. The Journal of Physical Chemistry C, Vol. 121, Issue 51 https://doi.org/10.1021/acs.jpcc.7b07360	journal	December 2017
Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability Baker, Andrew M.; Williams, Stefan T. D.; Mukundan, Rangachary Journal of Materials Chemistry A, Vol. 5, Issue 29 https://doi.org/10.1039/C7TA03452K	journal	January 2017
Local Degradation at Membrane Defects in Polymer Electrolyte Fuel Cells Kreitmeier, Stefan; Lerch, Philippe; Wokaun, Alexander Journal of The Electrochemical Society, Vol. 160, Issue 4 https://doi.org/10.1149/1.023306jes	journal	January 2013
Determination of Ce ³⁺ and Co ²⁺ Diffusion Coefficients in NR211 Membrane Coms, Frank D.; McQuarters, Ashley B. ECS Transactions, Vol. 86, Issue 13 https://doi.org/10.1149/08613.0395ecst	journal	July 2018
Cerium Migration during PEM Fuel Cell Accelerated Stress Testing Baker, Andrew M.; Mukundan, Rangachary; Spernjak, Dusan Journal of The Electrochemical Society, Vol. 163, Issue 9 https://doi.org/10.1149/2.0181609jes	journal	January 2016
The Chemistry of Fuel Cell Membrane Chemical Degradation Coms, Frank D. 214th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2981859	conference	January 2008
Development of Operando Confocal Microprobe X-ray Fluorescence Techniques to Measure Cation Transport in PEM Fuel Cells Baker, Andrew M.; Cai, Yun; Ziegelbauer, Joseph M. ECS Transactions, Vol. 92, Issue 8 https://doi.org/10.1149/09208.0107ecst	journal	July 2019
Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary Journal of The Electrochemical Society, Vol. 164, Issue 12 https://doi.org/10.1149/2.1221712jes	journal	January 2017
Mechanism of Perfluorsulfonic Acid Membrane Chemical Degradation Under Low RH Conditions Coms, F. D.; Xu, H.; McCallum, T. ECS Transactions, Vol. 50, Issue 2 https://doi.org/10.1149/05002.0907ecst	journal	March 2013
Fuel Cell Perfluorinated Sulfonic Acid Membrane Degradation Correlating Accelerated Stress Testing and Lifetime Rodgers, Marianne P.; Bonville, Leonard J.; Kunz, H. Russell Chemical Reviews, Vol. 112, Issue 11 https://doi.org/10.1021/cr200424d	journal	September 2012
A Critical Review of Modeling Transport Phenomena in Polymer-Electrolyte Fuel Cells Weber, Adam Z.; Borup, Rodney L.; Darling, Robert M. Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0751412jes	journal	January 2014
In-Situ Modeling of Chemical Membrane Degradation and Mitigation in Ceria-Supported Fuel Cells Wong, Ka Hung; Kjeang, Erik Journal of The Electrochemical Society, Vol. 164, Issue 12 https://doi.org/10.1149/2.1201712jes	journal	January 2017
Water Transport Behavior in Nafion 117 Membranes Xie, Gang Journal of The Electrochemical Society, Vol. 142, Issue 9 https://doi.org/10.1149/1.2048686	journal	January 1995
Degradation Mitigation in Polymer Electrolyte Membranes Using Cerium Oxide as a Regenerative Free-Radical Scavenger Trogadas, Panagiotis; Parrondo, Javier; Ramani, Vijay Electrochemical and Solid-State Letters, Vol. 11, Issue 7 https://doi.org/10.1149/1.2916443	journal	January 2008
Advanced Redox-Flow Batteries: A Perspective Perry, Mike L.; Weber, Adam Z. Journal of The Electrochemical Society, Vol. 163, Issue 1 https://doi.org/10.1149/2.0101601jes	journal	September 2015
Mitigation of Perfluorosulfonic Acid Membrane Chemical Degradation Using Cerium and Manganese Ions Coms, Frank D.; Liu, Han; Owejan, Jeanette E. 214th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2982015	conference	January 2008
The degradation mitigation effect of cerium oxide in polymer electrolyte membranes in extended fuel cell durability tests Pearman, Benjamin P.; Mohajeri, Nahid; Brooker, R. Paul Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.10.015	journal	March 2013
Unraveling the local energetics of transport in a polymer ion conductor Lingwood, Mark D.; Zhang, Zhiyang; Kidd, Bryce E. Chemical Communications, Vol. 49, Issue 39 https://doi.org/10.1039/c2cc37173a	journal	January 2013
Impact of CeOx Additives on Cathode Catalyst Layer Poisoning Banham, D.; Ye, S.; Cheng, T. ECS Transactions, Vol. 58, Issue 1 https://doi.org/10.1149/05801.0369ecst	journal	August 2013
Full Factorial Experiment to Determine and Predict Impact of Cerium Amount on Fuel Cell Performance Redmond, Erin L.; Wriston, Shirley; Szarka, John L. ECS Transactions, Vol. 80, Issue 8 https://doi.org/10.1149/08008.0633ecst	journal	August 2017
Progress Toward Accurate Through-Plane Ion Transport Resistance Measurement of Thin Solid Electrolytes Cooper, Kevin R. Journal of The Electrochemical Society, Vol. 157, Issue 11 https://doi.org/10.1149/1.3481561	journal	January 2010
A Mechanistic Study of Perfluorosulfonic Acid Membrane Water Permeance Degradation in Air Coms, Frank D.; Fuller, Timothy J.; Schaffer, Corey P. Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0141806jes	journal	January 2018
Cerium Migration through Hydrogen Fuel Cells during Accelerated Stress Testing Stewart, S. M.; Spernjak, D.; Borup, R. ECS Electrochemistry Letters, Vol. 3, Issue 4 https://doi.org/10.1149/2.008404eel	journal	January 2014
Chemical and Morphological Origins of Improved Ion Conductivity in Perfluoro Ionene Chain Extended Ionomers Su, Gregory M.; Cordova, Isvar A.; Yandrasits, Michael A. Journal of the American Chemical Society, Vol. 141, Issue 34 https://doi.org/10.1021/jacs.9b05322	journal	August 2019
Membrane Accelerated Stress Test Development for Polymer Electrolyte Fuel Cell Durability Validated Using Field and Drive Cycle Testing Mukundan, Rangachary; Baker, Andrew M.; Kusoglu, Ahmet Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0101806jes	journal	January 2018
Ion and Water Transport Characteristics in Membranes for Polymer Electrolyte Fuel Cells Containing H[sup +] and Ca[sup 2+] Cations Okada, Tatsuhiro Journal of The Electrochemical Society, Vol. 144, Issue 8 https://doi.org/10.1149/1.1837890	journal	January 1997
The ion and water transport properties of K+ and Na+ form perfluorosulfonic acid polymer Peng, Jing; Tian, Mengkun; Cantillo, Nelly M. Electrochimica Acta, Vol. 282 https://doi.org/10.1016/j.electacta.2018.06.035	journal	August 2018
New Insights into Perfluorinated Sulfonic-Acid Ionomers Kusoglu, Ahmet; Weber, Adam Z. Chemical Reviews, Vol. 117, Issue 3 https://doi.org/10.1021/acs.chemrev.6b00159	journal	January 2017
Estimation of Cation Contamination Level in Polymer Electrolyte Membrane Fuel Cells by Electrochemical Impedance Spectroscopy Shibata, Masao; Kitano, Naoki; Shinohara, Akihiro ECS Transactions, Vol. 85, Issue 13 https://doi.org/10.1149/08513.0905ecst	journal	June 2018
Modeling Coupled Durability and Performance in Polymer-Electrolyte Fuel Cells: Membrane Effects Ehlinger, Victoria M.; Kusoglu, Ahmet; Weber, Adam Z. Journal of The Electrochemical Society, Vol. 166, Issue 7 https://doi.org/10.1149/2.0281907jes	journal	January 2019
Membrane degradation during combined chemical and mechanical accelerated stress testing of polymer electrolyte fuel cells Lim, C.; Ghassemzadeh, L.; Van Hove, F. Journal of Power Sources, Vol. 257 https://doi.org/10.1016/j.jpowsour.2014.01.106	journal	July 2014
Proton Solvation and Transport in Aqueous and Biomolecular Systems: Insights from Computer Simulations Swanson, Jessica M. J.; Maupin, C. Mark; Chen, Hanning The Journal of Physical Chemistry B, Vol. 111, Issue 17 https://doi.org/10.1021/jp070104x	journal	May 2007
Structure/property relationship of Nafion XL composite membranes Shi, Shouwen; Weber, Adam Z.; Kusoglu, Ahmet Journal of Membrane Science, Vol. 516 https://doi.org/10.1016/j.memsci.2016.06.004	journal	October 2016
Mechanisms of Ion and Water Transport in Perfluorosulfonated Ionomer Membranes for Fuel Cells Saito, Morihiro; Arimura, Naoko; Hayamizu, Kikuko The Journal of Physical Chemistry B, Vol. 108, Issue 41 https://doi.org/10.1021/jp0482565	journal	October 2004
Study of Self-Diffusion of Monovalent and Divalent Cations in Nafion-117 Ion-Exchange Membrane Goswami, A.; Acharya, Anjali; Pandey, A. K. The Journal of Physical Chemistry B, Vol. 105, Issue 38 https://doi.org/10.1021/jp010529y	journal	September 2001
Water orientation and ion solvation effects during multicomponent salt partitioning in a Nafion cation exchange membrane Bontha, J. R.; Pintauro, P. N. Chemical Engineering Science, Vol. 49, Issue 23 https://doi.org/10.1016/0009-2509(94)00205-3	journal	January 1994
Computational study of the cerium(III) ion in aqueous environment Lutz, Oliver M. D.; Hofer, Thomas S.; Randolf, Bernhard R. Chemical Physics Letters, Vol. 539-540 https://doi.org/10.1016/j.cplett.2012.05.023	journal	June 2012
Development of a Method for Clarifying the Perfluorosulfonated Membrane Degradation Mechanism in a Fuel Cell Environment Hommura, Satoru; Kawahara, Kengo; Shimohira, Tetsuji Journal of The Electrochemical Society, Vol. 155, Issue 1 https://doi.org/10.1149/1.2800171	journal	January 2008
Mathematical Modeling of a Cation-Exchange Membrane Containing Two Cations Delacourt, Charles; Newman, John Journal of The Electrochemical Society, Vol. 155, Issue 11, p. B1210-B1217 https://doi.org/10.1149/1.2977960	journal	January 2008
Mathematical Modelling of Cation Contamination in a Proton-exchange Membrane Weber, A. Z.; Delacourt, C. Fuel Cells, Vol. 8, Issue 6 https://doi.org/10.1002/fuce.200800044	journal	December 2008
The Effect of Impurity Cations on the Transport Characteristics of Perfluorosulfonated Ionomer Membranes Okada, Tatsuhiro; Ayato, Yuusuke; Yuasa, Makoto The Journal of Physical Chemistry B, Vol. 103, Issue 17 https://doi.org/10.1021/jp983762d	journal	April 1999
Structure-Transport Relationship of Perfluorosulfonic-Acid Membranes in Different Cationic Forms Shi, Shouwen; Weber, Adam Z.; Kusoglu, Ahmet Electrochimica Acta, Vol. 220 https://doi.org/10.1016/j.electacta.2016.10.096	journal	December 2016
Kinetic Simulation of the Chemical Stabilization Mechanism in Fuel Cell Membranes Using Cerium and Manganese Redox Couples Gubler, Lorenz; Koppenol, Willem H. Journal of The Electrochemical Society, Vol. 159, Issue 2 https://doi.org/10.1149/2.075202jes	journal	January 2011
UV–visible spectroscopy method for screening the chemical stability of potential antioxidants for proton exchange membrane fuel cells Banham, Dustin; Ye, Siyu; Knights, Shanna Journal of Power Sources, Vol. 281 https://doi.org/10.1016/j.jpowsour.2015.02.002	journal	May 2015
A Molecular Dynamics Study of the Effects of V ²⁺ and V ³⁺ on the Local Structure of Hydrated Nafion Cui, Shengting; Paddison, Stephen J. The Journal of Physical Chemistry C, Vol. 119, Issue 23 https://doi.org/10.1021/acs.jpcc.5b02876	journal	June 2015
Diffusion and Interfacial Transport of Water in Nafion Zhao, Qiao; Majsztrik, Paul; Benziger, Jay The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp1112125	journal	March 2011
Multicomponent space-charge transport model for ion-exchange membranes Yang, Yahan; Pintauro, Peter N. AIChE Journal, Vol. 46, Issue 6 https://doi.org/10.1002/aic.690460610	journal	June 2000
In-situ diagnostics and degradation mapping of a mixed-mode accelerated stress test for proton exchange membranes Lai, Yeh-Hung; Fly, Gerald W. Journal of Power Sources, Vol. 274 https://doi.org/10.1016/j.jpowsour.2014.10.116	journal	January 2015
Simulation of Performance Tradeoffs in Ceria Supported Polymer Electrolyte Fuel Cells Wong, Ka Hung; Kjeang, Erik Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0771902jes	journal	January 2019
Ce Cation Migration and Diffusivity in Perfluorosulfonic Acid Fuel Cell Membranes Baker, Andrew M.; Komini Babu, Siddharth; Chintam, Kavitha ECS Transactions, Vol. 92, Issue 8 https://doi.org/10.1149/09208.0429ecst	journal	July 2019
Role of Mechanical Factors in Controlling the Structure–Function Relationship of PFSA Ionomers Kusoglu, Ahmet; Savagatrup, Suchol; Clark, Kyle T. Macromolecules, Vol. 45, Issue 18 https://doi.org/10.1021/ma301419s	journal	September 2012
Divalent/monovalent cation uptake selectivity in a Nafion cation-exchange membrane: Experimental and modeling studies Tandon, R.; Pintauro, P. N. Journal of Membrane Science, Vol. 136, Issue 1-2 https://doi.org/10.1016/S0376-7388(97)00167-1	journal	December 1997
Electrode Edge Cobalt Cation Migration in an Operating Fuel Cell: An In Situ Micro-X-ray Fluorescence Study Cai, Yun; Ziegelbauer, Joseph M.; Baker, Andrew M. Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0201806jes	journal	January 2018
Transport and equilibrium properties of Nafion® membranes with H+ and Na+ ions Okada, Tatsuhiro; Møller-Holst, Steffen; Gorseth, Oddvar Journal of Electroanalytical Chemistry, Vol. 442, Issue 1-2 https://doi.org/10.1016/S0022-0728(97)00499-3	journal	January 1998
Effect of cations (Na+, Ca2+, Fe3+) on the conductivity of a Nafion membrane Hongsirikarn, Kitiya; Goodwin, James G.; Greenway, Scott Journal of Power Sources, Vol. 195, Issue 21 https://doi.org/10.1016/j.jpowsour.2010.05.005	journal	November 2010
Ion and water transport characteristics of Nafion membranes as electrolytes Okada, Tatsuhiro; Xie, Gang; Gorseth, Oddvar Electrochimica Acta, Vol. 43, Issue 24 https://doi.org/10.1016/S0013-4686(98)00132-7	journal	August 1998
Accelerated Stress Testing of Fuel Cell Membranes Subjected to Combined Mechanical/Chemical Stressors and Cerium Migration Lai, Yeh-Hung; Rahmoeller, Kenneth M.; Hurst, James H. Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0241806jes	journal	January 2018
Radical (HO●, H● and HOO●) Formation and Ionomer Degradation in Polymer Electrolyte Fuel Cells Gubler, Lorenz; Dockheer, Sindy M.; Koppenol, Willem H. Journal of The Electrochemical Society, Vol. 158, Issue 7 https://doi.org/10.1149/1.3581040	journal	January 2011
Migration of Ce and Mn Ions in PEMFC and Its Impact on PFSA Membrane Degradation Zatoń, Marta; Prélot, Benedicte; Donzel, Nicolas Journal of The Electrochemical Society, Vol. 165, Issue 6 https://doi.org/10.1149/2.0311806jes	journal	January 2018

Similar Records

Comparison of the Hydration and Diffusion of Protons in Perfluorosulfonic Acid Membranes with Molecular Dynamics Simulations

Journal Article · Thu Oct 23 00:00:00 EDT 2008 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1783118

Cui, Shengting; Liu, Junwu; Selvan, Myvizhi Esai; +3 more

Improved Ionomers and Membranes for Fuel Cells

Technical Report · Thu Jun 08 00:00:00 EDT 2023 · OSTI ID:1783118

Topping, Chris; Jayasinghe, Rahula; Wasilewski, Matt; +7 more

Impact of Dispersion Solvent on Ionomer Thin Films and Membranes

Journal Article · Mon Nov 23 00:00:00 EST 2020 · ACS Applied Polymer Materials · OSTI ID:1783118

Berlinger, Sarah A.; Dudenas, Peter J.; Bird, Ashley; +5 more

Related Subjects

36 MATERIALS SCIENCE
ionomers
structure-property relationships
cation doping
concentrated solution theory
ion transport
Energy Sciences
Fuel Cell
Durability
cerium
Polymer electrolyte

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

Citation Formats

References (64)

Similar Records

Related Subjects

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