Morphology and Transport Study of Acid-Base Blend Proton Exchange Membranes by Molecular Simulations: Case of Chitosan/Nafion.

Blending a basic polymer (e.g., chitosan) with Nafion can modify some membrane properties in direct methanol fuel cell applications, e.g., controlling methanol crossover, by regulating the morphology of hydrophilic channels. Unraveling the mechanisms by which the channel morphology is modified is essential to formulate design strategies for acid-base blend membrane development. Thus, we use molecular simulations to analyze the morphological features of a blend membrane (at 75/25 chitosan/Nafion wt %), i.e., (i) water/polymer phase organizations, (ii) number and size of water clusters, and (iii) quantitative morphological measures of hydrophilic channels, and compare them to the pure Nafion in a wide range of water contents. It is found that the affinity of water to different hydrophilic groups in the blend membrane can result in more distorted and dispersed hydrophilic phase and fewer bulk water-like features compared to pure Nafion. Also, the width of the hydrophilic network bottleneck, i.e., pore limiting diameter (PLD), is found to be almost five times smaller for the blend membrane compared to Nafion at their maximum water contents. Moreover, by changing the chitosan/Nafion weight ratio from 75/25 to 0/100, we show that as Nafion content increases, all channel morphological characteristics alter monotonically except PLD. This is mainly due to the strong acid-base interactions between Nafion and chitosan, which hinder the monotonic growth of PLD. Interestingly, water and methanol diffusion coefficients are strongly correlated with PLD, suggesting that PLD can be used as a single parameter for tailoring the blending ratio for achieving the desired diffusion properties of acid-base membranes.