Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation
Abstract
Multicomponent mass-transport in cation-exchange membranes involves the movement of multiple species whose motion is coupled one to another. This phenomenon mediates the performance of numerous electrochemical and water purification technologies. This work presents and validates against experiment a mathematical model for multicomponent mass transport in phase-separated cation-exchange membranes (e.g., perfluorinated sulfonic-acid ionomers). Stefan-Maxwell-Onsager theory describes concentrated-solution transport. Hydrodynamic theory provides constitutive relations for the solute/solvent, solute/membrane, and solvent/membrane friction coefficients. Classical porous-medium theories scale membrane tortuosity. Electrostatic relaxation creates friction between ions. The model uses calculated ion and solvent partitioning between the external solution and the membrane from Part I of this series and incorporates the corresponding ion speciation into the transport coefficients. The proposed transport model compares favorably to properties (e.g., membrane conductivity, transference numbers, electroosmosis, and permeability) measured in dilute and concentrated aqueous binary and ternary electrolytes. The results reveal that the concentration and type of ions in the external solution alter the solvent volume fraction and viscosity in the hydrophilic pathways of the membrane, changing macroscale ionomer conductivity, permeability, and transference numbers. This work provides a physicochemical framework to predict ion-exchange-membrane performance in multicomponent systems exhibiting coupled transport.
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1598404
- Alternate Identifier(s):
- OSTI ID: 1619148
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society (Online)
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society (Online) Journal Volume: 167 Journal Issue: 1; Journal ID: ISSN 1945-7111
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE
Citation Formats
Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., and Weber, Adam Z. Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/ab6724.
Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., & Weber, Adam Z. Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation. United States. https://doi.org/10.1149/1945-7111/ab6724
Crothers, Andrew R., Darling, Robert M., Kusoglu, Ahmet, Radke, Clayton J., and Weber, Adam Z. Wed .
"Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation". United States. https://doi.org/10.1149/1945-7111/ab6724.
@article{osti_1598404,
title = {Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation},
author = {Crothers, Andrew R. and Darling, Robert M. and Kusoglu, Ahmet and Radke, Clayton J. and Weber, Adam Z.},
abstractNote = {Multicomponent mass-transport in cation-exchange membranes involves the movement of multiple species whose motion is coupled one to another. This phenomenon mediates the performance of numerous electrochemical and water purification technologies. This work presents and validates against experiment a mathematical model for multicomponent mass transport in phase-separated cation-exchange membranes (e.g., perfluorinated sulfonic-acid ionomers). Stefan-Maxwell-Onsager theory describes concentrated-solution transport. Hydrodynamic theory provides constitutive relations for the solute/solvent, solute/membrane, and solvent/membrane friction coefficients. Classical porous-medium theories scale membrane tortuosity. Electrostatic relaxation creates friction between ions. The model uses calculated ion and solvent partitioning between the external solution and the membrane from Part I of this series and incorporates the corresponding ion speciation into the transport coefficients. The proposed transport model compares favorably to properties (e.g., membrane conductivity, transference numbers, electroosmosis, and permeability) measured in dilute and concentrated aqueous binary and ternary electrolytes. The results reveal that the concentration and type of ions in the external solution alter the solvent volume fraction and viscosity in the hydrophilic pathways of the membrane, changing macroscale ionomer conductivity, permeability, and transference numbers. This work provides a physicochemical framework to predict ion-exchange-membrane performance in multicomponent systems exhibiting coupled transport.},
doi = {10.1149/1945-7111/ab6724},
journal = {Journal of the Electrochemical Society (Online)},
number = 1,
volume = 167,
place = {United States},
year = {2020},
month = {1}
}
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https://doi.org/10.1149/1945-7111/ab6724
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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
Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology
journal, October 2004
- Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
- Chemical Reviews, Vol. 104, Issue 10
Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part III. Transport in Vanadium Redox-Flow-Battery Separators
journal, January 2020
- Crothers, Andrew R.; Darling, Robert M.; Kushner, Douglas I.
- Journal of The Electrochemical Society, Vol. 167, Issue 1
Simulation of the Direct Methanol Fuel Cell
journal, January 2002
- Meyers, Jeremy P.; Newman, John
- Journal of The Electrochemical Society, Vol. 149, Issue 6
Hydrodynamic models for diffusion in microporous membranes
journal, March 1976
- Lightfoot, Edwin N.; Bassingthwaighte, James B.; Grabowski, Eric F.
- Annals of Biomedical Engineering, Vol. 4, Issue 1
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
Irreversible thermodynamics of transport across charged membranes
journal, February 1987
- Narȩbska, Anna; Kujawski, Wojciech; Koter, Sanisław
- Journal of Membrane Science, Vol. 30, Issue 2
Role of convection and related effects on species crossover and capacity loss in vanadium redox flow batteries
journal, September 2012
- Knehr, K. W.; Kumbur, E. C.
- Electrochemistry Communications, Vol. 23
Species Uptake and Mass Transport in Membranes for Vanadium Redox Flow Batteries
journal, May 2017
- Elgammal, Ramez A.; Tang, Zhijiang; Sun, Che-Nan
- Electrochimica Acta, Vol. 237
A modified Maxwell-Stefan model for transport through inert membranes: the binary friction model
journal, December 1996
- Kerkhof, Piet J. A. M.
- The Chemical Engineering Journal and the Biochemical Engineering Journal, Vol. 64, Issue 3
Composition and Conductivity of Membranes Equilibrated with Solutions of Sulfuric Acid and Vanadyl Sulfate
journal, January 2013
- Tang, Zhijiang; Svoboda, Rachel; Lawton, Jamie S.
- Journal of The Electrochemical Society, Vol. 160, Issue 9
Transport of electrolytes in charged pores: Analysis using the method of spatial averaging
journal, May 1989
- Hawkins Cwirko, E.; Carbonell, R. G.
- Journal of Colloid and Interface Science, Vol. 129, Issue 2
Proton Solvation and Transport in Realistic Proton Exchange Membrane Morphologies
journal, February 2016
- Savage, John; Voth, Gregory A.
- The Journal of Physical Chemistry C, Vol. 120, Issue 6
Continuum transport laws for locally non-neutral concentrated electrolytes
journal, December 2013
- Monroe, Charles W.; Delacourt, Charles
- Electrochimica Acta, Vol. 114
A Transient Vanadium Flow Battery Model Incorporating Vanadium Crossover and Water Transport through the Membrane
journal, January 2012
- Knehr, K. W.; Agar, Ertan; Dennison, C. R.
- Journal of The Electrochemical Society, Vol. 159, Issue 9
Transport in Polymer-Electrolyte Membranes
journal, January 2004
- Weber, Adam Z.; Newman, John
- Journal of The Electrochemical Society, Vol. 151, Issue 2
Transport Property Requirements for Flow Battery Separators
journal, July 2015
- Darling, Robert; Gallagher, Kevin; Xie, Wei
- Journal of The Electrochemical Society, Vol. 163, Issue 1
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
The Influence of Electric Field on Crossover in Redox-Flow Batteries
journal, July 2015
- Darling, Robert M.; Weber, Adam Z.; Tucker, Michael C.
- Journal of The Electrochemical Society, Vol. 163, Issue 1
Tortuosity in Porous Media: A Critical Review
journal, January 2013
- Ghanbarian, Behzad; Hunt, Allen G.; Ewing, Robert P.
- Soil Science Society of America Journal, Vol. 77, Issue 5
New Foundations of Newman’s Theory for Solid Electrolytes: Thermodynamics and Transient Balances
journal, January 2017
- Goyal, Priyamvada; Monroe, Charles W.
- Journal of The Electrochemical Society, Vol. 164, Issue 11
Ion and Water Transport Characteristics of Perfluorosulfonated Ionomer Membranes with H + and Alkali Metal Cations
journal, February 2002
- Okada, Tatsuhiro; Satou, Hiroyuki; Okuno, Mitsuhiro
- The Journal of Physical Chemistry B, Vol. 106, Issue 6
Structural and transport properties of Nafion in hydrobromic-acid solutions
journal, December 2013
- Kusoglu, Ahmet; Cho, Kyu Taek; Prato, Rafael A.
- Solid State Ionics, Vol. 252
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
Onsager Reciprocal Relations for Stefan−Maxwell Diffusion
journal, July 2006
- Monroe, Charles W.; Newman, John
- Industrial & Engineering Chemistry Research, Vol. 45, Issue 15
Proton Exchange Membrane Performance Characterization in VRFB
conference, January 2012
- Tang, Zhijiang; Keith, Rachel; Aaron, Douglas S.
- 220th ECS Meeting, ECS Transactions
Design of an Electrochemical Cell Making Syngas (CO + H2) from CO2 and H2O Reduction at Room Temperature
journal, January 2008
- Delacourt, Charles; Ridgway, Paul L.; Kerr, John B.
- Journal of The Electrochemical Society, Vol. 155, Issue 1, p. B42-B49
Mass transport of electrolytes in membranes. 1. Development of mathematical transport model
journal, May 1984
- Pintauro, Peter N.; Bennion, Douglas N.
- Industrial & Engineering Chemistry Fundamentals, Vol. 23, Issue 2
Soil properties influencing apparent electrical conductivity: a review
journal, March 2005
- Friedman, Shmulik P.
- Computers and Electronics in Agriculture, Vol. 46, Issue 1-3
Mass transport of electrolytes in membranes. 2. Determination of sodium chloride equilibrium and transport parameters for Nafion
journal, May 1984
- Pintauro, Peter N.; Bennion, Douglas N.
- Industrial & Engineering Chemistry Fundamentals, Vol. 23, Issue 2
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
Steady-state diffusion of water through soft-contact-lens materials
journal, October 2005
- Fornasiero, Francesco; Krull, Florian; Prausnitz, John M.
- Biomaterials, Vol. 26, Issue 28
Ion Effects on Vanadium Transport in Nafion Membranes for Vanadium Redox Flow Batteries
journal, January 2017
- Lawton, Jamie S.; Jones, Amanda M.; Tang, Zhijiang
- Journal of The Electrochemical Society, Vol. 164, Issue 13
New Insights into Perfluorinated Sulfonic-Acid Ionomers
journal, January 2017
- Kusoglu, Ahmet; Weber, Adam Z.
- Chemical Reviews, Vol. 117, Issue 3
Concentrated Solution Model of Transport in All Vanadium Redox Flow Battery Membrane Separator
journal, September 2014
- Ashraf Gandomi, Y.; Zawodzinski, T. A.; Mench, M. M.
- ECS Transactions, Vol. 61, Issue 13
Theory of Ion and Water Transport in Reverse-Osmosis Membranes
journal, February 2018
- Oren, Y. S.; Biesheuvel, P. M.
- Physical Review Applied, Vol. 9, Issue 2
Electrochemical Synthesis of Ammonia: A Low Pressure, Low Temperature Approach
journal, January 2015
- Renner, J. N.; Greenlee, L. F.; Ayres, K. E.
- Interface magazine, Vol. 24, Issue 2
On the Gibbs-Duhem equation for thermodynamic systems of mixed Euler order with special reference to gravitational and nonelectroneutral systems
journal, January 1997
- Sørensen, Torben Smith; Compañ, Vicente
- Electrochimica Acta, Vol. 42, Issue 4
Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review
journal, June 2016
- Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael
- ChemSusChem, Vol. 9, Issue 13
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
The water content dependence of electro-osmotic drag in proton-conducting polymer electrolytes
journal, February 1995
- Zawodzinski, Thomas A.; Davey, John; Valerio, Judith
- Electrochimica Acta, Vol. 40, Issue 3
Multicomponent Space-Charge Transport Model for Ion-Exchange Membranes with Variable Pore Properties
journal, June 2004
- Yang, Y.; Pintauro, P. N.
- Industrial & Engineering Chemistry Research, Vol. 43, Issue 12
Mathematical Modelling of Cation Contamination in a Proton-exchange Membrane
journal, December 2008
- Weber, A. Z.; Delacourt, C.
- Fuel Cells, Vol. 8, Issue 6
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
Structure-Transport Relationship of Perfluorosulfonic-Acid Membranes in Different Cationic Forms
journal, December 2016
- Shi, Shouwen; Weber, Adam Z.; Kusoglu, Ahmet
- Electrochimica Acta, Vol. 220
Towards membrane-electrode assembly systems for CO 2 reduction: a modeling study
journal, January 2019
- Weng, Lien-Chun; Bell, Alexis T.; Weber, Adam Z.
- Energy & Environmental Science, Vol. 12, Issue 6
Multicomponent Diffusion
journal, July 1999
- Curtiss, C. F.; Bird, R. Byron
- Industrial & Engineering Chemistry Research, Vol. 38, Issue 7
Coupled Membrane Transport Parameters for Ionic Species in All-Vanadium Redox Flow Batteries
journal, November 2016
- Ashraf Gandomi, Yasser; Aaron, D. S.; Mench, M. M.
- Electrochimica Acta, Vol. 218
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
Membrane transport characteristics of binary cation systems with Li+ and alkali metal cations in perfluorosulfonated ionomer
journal, May 2005
- Okada, Tatsuhiro; Arimura, Naoko; Satou, Hiroyuki
- Electrochimica Acta, Vol. 50, Issue 16-17
Fundamental water and salt transport properties of polymeric materials
journal, January 2014
- Geise, Geoffrey M.; Paul, Donald R.; Freeman, Benny D.
- Progress in Polymer Science, Vol. 39, Issue 1
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
The Maxwell-Stefan approach to mass transfer
journal, March 1997
- Krishna, R.; Wesselingh, J. A.
- Chemical Engineering Science, Vol. 52, Issue 6
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
Selectivity of ion exchange membranes: A review
journal, June 2018
- Luo, Tao; Abdu, Said; Wessling, Matthias
- Journal of Membrane Science, Vol. 555
Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions
journal, November 2009
- Bazant, Martin Z.; Kilic, Mustafa Sabri; Storey, Brian D.
- Advances in Colloid and Interface Science, Vol. 152, Issue 1-2
Transport of simple electrolyte solutions through ion-exchange membranes—the capillary model
journal, August 2002
- Koter, Stanisław
- Journal of Membrane Science, Vol. 206, Issue 1-2
Exploring the Maxwell-Stefan description of ion exchange
journal, April 1995
- Wesselingh, J. A.; Vonk, P.; Kraaijeveld, G.
- The Chemical Engineering Journal and the Biochemical Engineering Journal, Vol. 57, Issue 2
Nernst-Planck transport theory for (reverse) electrodialysis: I. Effect of co-ion transport through the membranes
journal, July 2016
- Tedesco, M.; Hamelers, H. V. M.; Biesheuvel, P. M.
- Journal of Membrane Science, Vol. 510
Insights into membrane-separated organic electrosynthesis: the case of adiponitrile electrochemical production
journal, January 2020
- Blanco, Daniela E.; Prasad, Purnima A.; Dunningan, Kaylee
- Reaction Chemistry & Engineering, Vol. 5, Issue 1
Modeling of vanadium ion diffusion across the ion exchange membrane in the vanadium redox battery
journal, May 2012
- Skyllas-Kazacos, Maria; Goh, Leesean
- Journal of Membrane Science, Vol. 399-400