DOE OSTI2012
Concerns over global climate change associated with fossil-fuel consumption continue to drive the development of electrochemical alternatives for energy technology. Proton exchange fuel cells are a particularly promising technology for stationary power generation, mobile electronics, and hybrid engines in automobiles. For these devices to work efficiently, direct electrical contacts between the anode and cathode must be avoided; hence, the separator material must be electronically insulating but highly proton conductive. As a result, researchers have examined a variety of polymer electrolyte materials for use as membranes in these systems. In the optimization of the membrane, researchers are seeking high proton conductivity, low electronic conduction, and mechanical stability with the inclusion of water in the polymer matrix. A considerable number of potential polymer backbone and side chain combinations have been synthesized to meet these requirements, and computational studies can assist in the challenge of designing the next generation of technologically relevant membranes. Such studies can also be integrated in a feedback loop with experiment to improve fuel cell performance. However, to accurately simulate the currently favored class of membranes, perfluorosulfonic acid containing moieties, several difficulties must be addressed including a proper treatment of the proton-hopping mechanism through the membrane and the formation of nanophase-separated water networks. We discuss our recent efforts to address these difficulties using methods that push the limits of computer simulation and expand on previous theoretical developments. We describe recent advances in the multistate empirical valence bond (MS-EVB) method that can probe proton diffusion at the nanometer-length scale and accurately model the so-called Grotthuss shuttling mechanism for proton diffusion in water. Using both classical molecular dynamics and coarse-grained descriptions that replace atomistic representations with collective coordinates, we investigated the proton conductivity of polymer membrane structure as a function of hydration level. Nanometer-sized water channels form torturous pathways that are traversed by the charges during fuel cell operation. Using a combination of coarse-grained membrane structure and novel multiscale methods, we demonstrate emerging approaches to treat proton motion at the mesoscale in these complex materials.