Dissipative Particle Dynamics Modeling of Polyelectrolyte Membrane-Water Interfaces.

Previous experiments of water vapor penetration into polyelectrolyte membrane (PEM) thin films have indicated the influence of the water concentration gradient and polymer chemistry on the interface evolution, which will eventually affect the efficiency of the fuel cell operation. Moreover, PEMs of different side chains have shown differences in water cluster structure and diffusion. The evolution of the interface between water and polyelectrolyte membranes (PEMs), which are used in fuel cells and flow batteries, of three different side-chain lengths has been studied using dissipative particle dynamics (DPD) simulations. Higher and faster water uptake is usually beneficial in the operation of fuel cells and flow batteries. The simulated water uptake increased with the increasing side chain length. In addition, the water uptake was rapid initially and slowed down afterwards, which is in agreement with the experimental observations. The water cluster formation rate was also found to increase with the increasing side-chain length, whereas the water cluster shapes were unaffected. Water diffusion in the membranes, which affects proton mobility in the PEMs, increased with the side-chain length at all distances from the interface. In conclusion, side-chain length was found to have a strong influence on the interface water structure and water penetration rates, which can be harnessed for the better design of PEMs. Since the PEM can undergo cycles of dehydration and rehydration, faster water uptake increases the efficiency of these devices. We show that the longer side chains with backbone structure similar to Nafion should be more suitable for fuel cell/flow battery usage.

Molecular Modeling of Structure and Dynamics of Nafion Protonation States.

We present the results of the atomistic molecular dynamics modeling of different protonation states of Nafion at varying hydration levels. Previous experiments have shown that the degree of deprotonation (DDP) of the sulfonic acid groups in a Nafion membrane varies significantly upon hydration. Our goal is to provide insights into the effects of variable protonation states and water content on the internal structure and vehicular transport inside the Nafion membrane. The Nafion side chain lengths showed a weak increasing trend with increasing DDP at all hydration levels, exposing more of the sulfonic acid groups to the hydrophilic/water phase. The water-phase characteristic size/diameter decreased with increasing DDP, but, interestingly, the average number of water molecules per cluster increased. The probability of water-hydronium hydrogen bond formation decreased with increasing DDP, despite an increase in the total number of such hydrogen bonds. The water diffusion was largely unaffected by the state of deprotonation. In contrast to that, the hydronium ion diffusion slowed down with increasing DDP in the overall membrane. The hydronium ion residence times around the sulfonic acid group increased with increasing DDP. Our simulations show a strong connection between the morphology of the water domains and protonation states of Nafion. Such a connection can also be expected in polyelectrolyte membranes similar to Nafion.

Molecular Dynamics Simulations of Substrate Hydrophilicity and Confinement Effects in Capped Nafion Films.

Nafion nanocomposites for energy-related applications are being used extensively because of the attractive properties such as enhanced water retention, low unwanted crossover of electrolytes, and high proton conductivity. We present the results of the molecular dynamics modeling of Nafion films confined between two walls (substrates) of different polymer-wall interaction strengths and of different separation distances to model Nafion nanocomposites. Our goal is to provide insights into the effects of varying hydrophilicity and volume fraction of fillers/nanoparticles on the internal structure and water transport inside the Nafion membrane. The sulfur-sulfur radial distribution function first peak distance and the sulfur-oxygen (water) coordination number in the first hydration shell were negligibly affected by the wall (substrate) hydrophilicity or the film thickness. The Nafion side chains were found to bend toward the substrates with high hydrophilicity which is in qualitative agreement with existing experiments. The amount of bending was observed to reduce with increasing film thickness. However, the side-chain length did not show any noticeable variation with wall (substrate) hydrophilicity or film thickness. The water clusters became smaller and more isolated clusters emerged for highly hydrophilic substrates. In addition, the water cluster sizes showed a decreasing trend with decreasing film thickness in the case of hydrophilic substrates, which has also been observed in experiments of supported Nafion films. The in-plane water diffusion was enhanced considerably for hydrophilic substrates, and this mechanism has also been proposed previously in experiments. The in-plane water diffusion was also found to be a strong function of the substrate selectivity toward the hydrophilic phase. Our simulations can help provide more insights to experimentalists for choosing or modifying nanoparticles for Nafion nanocomposites.