The Fickian diffusivity of water in Nafion has been shown to exhibit a local maximum. In the present research effort it is shown that this spike vanishes if the equilibrium water content and chemical diffusivity are modeled carefully. Further, it is shown that permeation experiments falsely can generate a local maximum, if a wrong equilibrium water content relation is used. Finally, in order to study the obtained diffusivity model a parameter variation is carried out using a one-dimensional steady-state model. The effect of diffusivity model, surface roughness and water content driving force is studied.
IntroductionAn issue of great importance in fuel cell commercialization is the understanding of water transport in the membrane. Water transport is governed by several mechanisms: diffusion, electro-osmotic drag (EOD), hydraulic permeation, swelling and interfacial resistance. Particularly, the Fickian diffusivity of water has been intensively discussed during the last decade due to inconsistencies in the reported values and dependencies on water content. Differences in the order of three decades have been reported, depending on the measurement technique employed (i.e. NMR-relaxation, mass sorption/desorption and permeation). In the study by Majsztrik et al. (1) it was shown that the latter two techniques essentially measure a combination of transport mechanisms, i.e. swelling, non-equilibrium interfacial resistance and diffusion. For permeation experiments the limiting resistance was shown to be the interfacial resistance, and for mass sorption/desorption experiments the limiting resistance was shown to be a combination of interfacial resistance and membrane swelling.Meanwhile, NMR-relaxation avoids these issues by directly measuring the selfdiffusion inside a membrane. However, when one wants to relate the chemical diffusivity to a Fickian, the diffusivity changes it apparent shape quiet drastically in that it suddenly contains a large spike (2).In the present research effort it will be argued that the very existence of such a spike is merely a mathematical artifact of its derivation. Moreover, a new diffusivity model without the spike present is validated against experimental measurements of the water content distribution through a one-dimensional diffusion model with non-equilibrium sorption/desorption based on the uptake model by Ge et al. (3). Moreover, using the onedimensional model, it is shown that permeation experiments falsely can generate a local maximum. Finally, the proposed diffusivity model is compared with models published in the literature through a parameter study. In particular the interaction between the diffusivity and the sorption/desorption is analyzed. 10.1149/05002.0979ecst ©The Electrochemical Society ECS Transactions, 50 (2) 979-991 (2012) 979 ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.111.121.42 Downloaded on 2015-07-05 to IP
TheoryThere are two terms that contribute to the observation of a local m...