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Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: Phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

Published online by Cambridge University Press:  07 June 2012

Ram Devanathan ,
Nagesh Idupulapati  and
Michel Dupuis
Ram Devanathan*
Affiliation:
Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352
Nagesh Idupulapati
Affiliation:
Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352
Michel Dupuis
Affiliation:
Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol, and hydronium in phenylated sulfonated poly(ether ether ketone ketone) (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. In Ph-SPEEKK, the average pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower relative to the corresponding properties in Nafion at comparable hydration levels. The aromatic carbon backbone of Ph-SPEEKK is more rigid and less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation in Ph-SPEEKK occurs at a hydration level (λ) of ∼8 H2O/SO3−. At λ = 20, water, methanol, and hydronium diffusion coefficients were 1.4 × 10−5, 0.6 × 10−5, and 0.2 × 10−5 cm2/s, respectively. For λ > 20, wide pores develop leading to an increase in methanol crossover and ion transport.

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Articles
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Journal of Materials Research , Volume 27 , Issue 15: Focus Issue: Advanced Materials for Fuel Cells , 14 August 2012 , pp. 1927 - 1938
Copyright
Copyright © Materials Research Society 2012

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