Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp400693g· OSTI ID:1512303
 [1];  [2];  [3];  [4]
  1. Colorado School of Mines, Golden, CO (United States). Renewable Energy Materials Research Science and Engineering Center; Univ. of Chicago, IL (United States). James Franck Inst., and Computation Inst., Dept. of Chemistry; University of Chicago
  2. Colorado School of Mines, Golden, CO (United States). Renewable Energy Materials Research Science and Engineering Center, Dept. of Chemical and Biological Engineering
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States). Computational Science Center
  4. Univ. of Chicago, IL (United States). James Franck Inst., and Computation Inst., Dept. of Chemistry
+ Show Author Affiliations
Proton transfer and local structures in 3M (EW 825) and Nafion (EW 890) membranes are investigated in this study by both standard nonreactive molecular dynamics and the self-consistent iterative multistate empirical valence bond method, which is capable of simulating multiple reactive protons and accounting for the Grotthuss mechanism of proton transport. The Nafion and 3M systems have the same backbone, so we can isolate and compare the effect of the different side chains by calculating the radial distribution functions (RDFs), self-diffusion constants, and other properties for three hydration levels at 5, 9, and 14 at 300 and 353 K. The conformations of the 3M and Nafion side chains are also compared. We found that even though many results are similar for both F3C and SPC/Fw water models, certain trends such as the sulfonate clustering can depend on the water model selected. The relationship between the different RDFs for the sulfonate, water, and hydronium is discussed. The self-diffusion constants of water for both membranes are found to be close with respect to each water model selected, even though the experimental values for 3M at 300 K are higher. In conclusion, the calculated self-diffusion constants of the excess protons are found to be higher for 3M than Nafion for hydration levels 9 and 14 at 300 K but statistically the same at 353 K.
Research Organization:
Univ. of Chicago, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
SC0005418
OSTI ID:
1512303
Alternate ID(s):
OSTI ID: 1582232
OSTI ID: 1082583
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 16 Vol. 117; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (45)

Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
On the development of proton conducting materials for technological applications journal May 1997
On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells journal April 2001
Short-side-chain proton conducting perfluorosulfonic acid ionomers: Why they perform better in PEM fuel cells journal April 2008
The effects of backbone conformation on hydration and proton transfer in the ‘short-side-chain’ perfluorosulfonic acid membrane journal October 2006
Investigation of proton diffusion in Nafion®117 membrane by electrical conductivity and NMR journal May 2009
An ab initio study of the primary hydration and proton transfer of CF3SO3H and CF3O(CF2)2SO3H: Effects of the hybrid functional and inclusion of diffuse functions journal September 2011
The effect of side chain connectivity and local hydration on proton transfer in 3M perfluorosulfonic acid membranes journal April 2012
State of Understanding of Nafion journal October 2004
Determination of water diffusion coefficients in perfluorosulfonate ionomeric membranes journal July 1991
DREIDING: a generic force field for molecular simulations journal December 1990
Interplay between Structure and Relaxations in Perfluorosulfonic Acid Proton Conducting Membranes journal December 2012
Nanophase-Segregation and Transport in Nafion 117 from Molecular Dynamics Simulations:  Effect of Monomeric Sequence journal March 2004
Dynamic Behavior of Water within a Polymer Electrolyte Fuel Cell Membrane at Low Hydration Levels journal January 2005
Molecular Modeling of the Short-Side-Chain Perfluorosulfonic Acid Membrane journal August 2005
Characterization of the Solvation and Transport of the Hydrated Proton in the Perfluorosulfonic Acid Membrane Nafion journal September 2006
Quasielastic Neutron Scattering Study of Water Dynamics in Hydrated Nafion Membranes journal January 2007
Proton Solvation and Transport in Hydrated Nafion journal May 2011
Effects of Polymer Morphology on Proton Solvation and Transport in Proton-Exchange Membranes journal August 2012
Molecular Modeling of Proton Transport in the Short-Side-Chain Perfluorosulfonic Acid Ionomer journal March 2008
An Improved Multistate Empirical Valence Bond Model for Aqueous Proton Solvation and Transport journal June 2008
Comparison of the Hydration and Diffusion of Protons in Perfluorosulfonic Acid Membranes with Molecular Dynamics Simulations journal October 2008
Molecular Dynamics Modeling of Proton Transport in Nafion and Hyflon Nanostructures journal May 2010
Probing Selected Morphological Models of Hydrated Nafion Using Large-Scale Molecular Dynamics Simulations journal March 2010
On the Relationship between Polymer Electrolyte Structure and Hydrated Morphology of Perfluorosulfonic Acid Membranes journal June 2010
Calibration and Testing of a Water Model for Simulation of the Molecular Dynamics of Proteins and Nucleic Acids in Solution journal June 1997
Multistate Empirical Valence Bond Model for Proton Transport in Water journal July 1998
Mesoscale Modeling of Hydrated Morphologies of 3M Perfluorosulfonic Acid-Based Fuel Cell Electrolytes journal September 2010
The Source of Helicity in Perfluorinated N -Alkanes journal July 2003
SANS Study of the Effects of Water Vapor Sorption on the Nanoscale Structure of Perfluorinated Sulfonic Acid (NAFION) Membranes journal July 2006
On the consequences of side chain flexibility and backbone conformation on hydration and proton dissociation in perfluorosulfonic acid membranes journal January 2006
Recent developments in proton exchange membranes for fuel cells journal January 2008
Insight from molecular modelling: does the polymer side chain length matter for transport properties of perfluorosulfonic acid membranes? journal January 2012
The effect of hydrogen bond reorganization and equivalent weight on proton transfer in 3M perfluorosulfonic acid ionomers journal January 2012
A second generation multistate empirical valence bond model for proton transport in aqueous systems journal September 2002
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I journal October 1955
A linear-scaling self-consistent generalization of the multistate empirical valence bond method for multiple excess protons in aqueous systems journal April 2005
Flexible simple point-charge water model with improved liquid-state properties journal January 2006
The computer simulation of proton transport in water journal November 1999
Proton Exchange Membranes for Fuel Cell Applications journal September 2006
Electro-osmosis in Nafion 117, Polystyrene Sulfonic Acid, and Polybenzimidazole journal January 2005
A Comparative Study of Water Uptake By and Transport Through Ionomeric Fuel Cell Membranes journal January 1993
The Development of New Membranes for Proton Exchange Membrane Fuel Cells conference January 2007
Proton Exchange Membranes for High Temperature Fuel Cells: Equivalent Weight and End Group Effects on Conductivity conference January 2009
Final Report - Membranes and MEA's for Dry, Hot Operating Conditions report June 2011

Cited By (5)

Understanding of Nanophase Separation and Hydrophilic Morphology in Nafion and SPEEK Membranes: A Combined Experimental and Theoretical Studies journal June 2019
Effects of water nanochannel diameter on proton transport in proton‐exchange membranes journal May 2019
Elucidating the morphological aspects and proton dynamics in a hybrid perfluorosulfonic acid membrane for medium-temperature fuel cell applications journal January 2018
Molecular Dynamics Modeling of the Conductivity of Lithiated Nafion Containing Nonaqueous Solvents journal January 2016
Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport journal January 2013

Figures / Tables (14)

Figure 1(p. 2)figure Figure 1
Figure 2(p. 3)figure Figure 2
Figure 3(p. 4)figure Figure 3
Table 1(p. 4)table Table 1
Figure 4(p. 5)figure Figure 4
Figure 5(p. 6)figure Figure 5
Figure 6(p. 6)figure Figure 6
Figure 7(p. 7)figure Figure 7
Figure 8(p. 8)figure Figure 8
Figure 9(p. 8)figure Figure 9
Figure 10(p. 9)figure Figure 10
Figure 11(p. 9)figure Figure 11
Figure 12(p. 10)figure Figure 12
Figure 13(p. 11)figure Figure 13

Similar Records

Proton Solvation and Transport in Hydrated Nafion
Journal Article · Thu Apr 21 00:00:00 EDT 2011 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1512298
Proton Solvation and Transport in Hydrated Nafion
Journal Article · Thu Apr 21 00:00:00 EDT 2011 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1582228

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY