Water Sorption, Desorption and Transport in Nafion Membranes

Water sorption, desorption, and permeation in and through Nafion 112, 115, 1110 and 1123 membranes were measured as functions of temperature between 30 and 90 ◦ C. Water permeation increased with temperature. Water permeation from liquid water increased with the water activity difference across the membrane. Water permeation from humidified gas into dry nitrogen went through a maximum with the water activity difference across the membrane. These results suggested that the membrane was less swollen in the presence of water vapor and that a thin skin formed on the dry side of the membrane that reduced permeability to water. Permeation was only weakly dependent on membrane thickness; results indicated that interfacial mass transport at the membrane/gas interface was the limiting resistance. The diffusivity of water in Nafion deduced from water sorption into a dry Nafion film was almost two orders of magnitude slower than the diffusivity determined from permeation experiments. The rate of water sorption did not scale with the membrane thickness as predicted by a Fickian diffusion analysis. The results indicated that water sorption was limited by the rate of swelling of the Nafion. Water desorption from a water saturated film was an order of magnitude faster than water sorption. Water desorption appeared to be limited by the rate of interfacial transport across the membrane/gas interface. The analysis of water permeation and sorption data identifies different regimes of water transport and sorption in Nafion membranes corresponding to diffusion through the membrane, interfacial transport across the membrane–gas interface and swelling of the polymer to accommodate water. © 2007 Elsevier B.V. All rights reserved.

[1]  Frano Barbir,et al.  PEM Fuel Cells: Theory and Practice , 2012 .

[2]  A. Goswami,et al.  Self-diffusion coefficients of water in Nafion-117 membrane with multivalent counterions , 2006 .

[3]  F. Thielmann,et al.  Measuring moisture sorption and diffusion kinetics on proton exchange membranes using a gravimetric vapor sorption apparatus , 2006 .

[4]  B. Seoane,et al.  Sorption and permeation of solutions of chloride salts, water and methanol in a Nafion membrane , 2006 .

[5]  Nikhil H. Jalani,et al.  Consideration of thermodynamic, transport, and mechanical properties in the design of polymer electrolyte membranes for higher temperature fuel cell operation , 2006 .

[6]  Andrew B. Bocarsly,et al.  Mechanical properties of Nafion and titania/Nafion composite membranes for polymer electrolyte membrane fuel cells , 2006 .

[7]  Hossein Toghiani,et al.  Investigation of water transport through membrane in a PEM fuel cell by water balance experiments , 2006 .

[8]  Denis Roizard,et al.  On Schroeder's paradox , 2006 .

[9]  Nikhil H. Jalani,et al.  The effect of equivalent weight, temperature, cationic forms, sorbates, and nanoinorganic additives on the sorption behavior of Nafion ® , 2005 .

[10]  I. Hsing,et al.  Absorption, Desorption, and Transport of Water in Polymer Electrolyte Membranes for Fuel Cells , 2005 .

[11]  Ravindra Datta,et al.  Thermodynamics and Proton Transport in Nafion I. Membrane Swelling, Sorption, and Ion-Exchange Equilibrium , 2005 .

[12]  J. Newman,et al.  Modeling Two-Phase Behavior in PEFCs , 2004 .

[13]  A. Weber,et al.  Modeling transport in polymer-electrolyte fuel cells. , 2004, Chemical reviews.

[14]  Shohji Tsushima,et al.  Water diffusion measurement in fuel-cell SPE membrane by NMR , 2004 .

[15]  Kinam Park,et al.  Reflexive Polymers and Hydrogels : Understanding and Designing Fast Responsive Polymeric Systems , 2004 .

[16]  N. Peppas.  Kinetics of smart hydrogels , 2004 .

[17]  Adam Z. Weber,et al.  Transport in Polymer-Electrolyte Membranes I. Physical Model , 2004 .

[18]  Ravindra Datta,et al.  Sorption in Proton-Exchange Membranes An Explanation of Schroeder’s Paradox , 2003 .

[19]  S. Srinivasan,et al.  A comparison of physical properties and fuel cell performance of Nafion and zirconium phosphate/Nafion composite membranes , 2003, physics/0310029.

[20]  L. Klein,et al.  Transport properties of Nafion™ composite membranes for proton-exchange membranes fuel cells , 2003 .

[21]  M. Douglas LeVan,et al.  Water transport properties of Nafion membranes. Part I. Single-tube membrane module for air drying , 2003 .

[22]  Yuichi Hirata,et al.  Sorption and diffusion behaviors of water in Nation 117 membranes with different counter ions , 2002 .

[23]  P. Krtil,et al.  Kinetics of Water Sorption in NafionThin Films − Quartz Crystal Microbalance Study , 2001 .

[24]  W. Wen,et al.  Self-diffusion of water, ethanol and decafluropentane in perfluorosulfonate ionomer by pulse field gradient NMR , 2001 .

[25]  K. Kreuer.  On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells , 2001 .

[26]  K. Fancey.  A Latch-Based Weibull Model for Polymerie Creep and Recovery , 2001 .

[27]  P. Gibson,et al.  Solubility and transport behavior of water and alcohols in Nafion , 2001 .

[28]  Sami Hietala,et al.  Sorption and diffusion of methanol and water in PVDF-g-PSSA and Nafion® 117 polymer electrolyte membranes , 2000 .

[29]  J. Newman,et al.  Equilibrium and diffusion of methanol and water in a nafion 117 membrane , 2000 .

[30]  J. Weidner,et al.  Diffusion of water in Nafion 115 membranes , 2000 .

[31]  R. Datta,et al.  Modeling of Conductive Transport in Proton-Exchange Membranes for Fuel Cells , 2000 .

[32]  James Larminie,et al.  Fuel Cell Systems Explained , 2000 .

[33]  Signe Kjelstrup,et al.  Transport and equilibrium properties of Nafion® membranes with H+ and Na+ ions , 1998 .

[34]  J. Schmelzer,et al.  Stress and time dependence of relaxation and the Kohlrausch stretched exponent formula , 1997 .

[35]  J. Hinatsu,et al.  Water Uptake of Perfluorosulfonic Acid Membranes from Liquid Water and Water Vapor , 1994 .

[36]  Xiaodong Sun,et al.  Water-sorption and transport properties of Nafion 117 H , 1993 .

[37]  Nikolaos A. Peppas,et al.  Modeling of penetrant diffusion in glassy polymers with an integral sorption deborah number , 1993 .

[38]  T. Springer,et al.  Water Uptake by and Transport Through Nafion® 117 Membranes , 1993 .

[39]  Mark W. Verbrugge,et al.  The Effect of Temperature on the Equilibrium and Transport Properties of Saturated Poly(perfluorosulfonic acid) Membranes , 1992 .

[40]  Shimshon Gottesfeld,et al.  Determination of water diffusion coefficients in perfluorosulfonate ionomeric membranes , 1991 .

[41]  T. Gierke,et al.  The Cluster—Network Model of Ion Clustering in Perfluorosulfonated Membranes , 1982 .

[42]  F. C. Wilson,et al.  Morphology of Perfluorosulfonated Membrane Products: Wide-Angle and Small-Angle X-Ray Studies , 1982 .

[43]  H. Yeager,et al.  Cation and Water Diffusion in Nafion Ion Exchange Membranes: Influence of Polymer Structure , 1981 .

[44]  Harry L. Frisch,et al.  Sorption and transport in glassy polymers-a review , 1980 .

[45]  A. Eisenberg,et al.  Sorption phenomena in nafion membranes , 1979 .

[46]  A. Eisenberg,et al.  Physical properties and supermolecular structure of perfluorinated ion‐containing (nafion) polymers , 1977 .

[47]  O. Levenspiel.  Chemical Reaction Engineering , 1972 .

[48]  John Crank,et al.  The Mathematics Of Diffusion , 1956 .