Proton Transport in Additives to the Polymer Electrolyte Membrane for Fuel Cell Application

Abstract

The enhancement of proton transport in polymer electrolyte membranes is an important issue for the development of fuel cell technology. The objective is a material providing proton transport at a temperature range of 350 K to 450 K independent from a purely water based mechanism. To enhance the PEM properties of standard polymer materials, a class of additives is studied by means of atomistic simulations consisting of functionalised mesoporous silicon dioxide particles. The functional molecules are imidazole or sulphonic acid, covalently bound to the surface via a carbon chain with a surface density of about 1.0 nm−2 groups. At first, the proton transport mechanism is explored in a system of functional molecules in vacuum. The molecules are constrained by the terminal carbon groups according to the geometric arrangement in the porous silicon dioxide. The proton transport mechanism is characterised by structural properties obtained from classical molecular dynamics simulations and consists of the aggregation of two or more functional groups, a barrier free proton transport between these groups followed by the separation of the groups and formation of new aggregates due to fluctuations in the hydrogen bond network and movement of the carbon chain. For the different proton conducting groups, i.e. methyl imidazole, methyl sulphonic acid and water, the barrier free proton transport and the formation of protonated bimolecular complexes were addressed by potential energy calculations of the density functional based tight binding method (DFTB). For sulphonic acid even at a temperature of 450 K, relatively stable aggregates are formed, while most imidazole groups are isolated and the hydrogen bond fluctuations are high. However, high density of groups and elevated temperatures enhance the proton transport in both systems. Besides the anchorage and the density of the groups, the influence of the chemical environment on the proton transport was studied. Therefore, the uptake and distribution of water molecules was estimated from classical molecular dynamic simulations and the local chemical environment was determined for different functional groups. The sulphonic acid functionalised silicon dioxide pores are more hydrophilic than the unfunctionalised and the imidazole functionalised systems. At lower hydration, the distribution of water is inhomogeneous and the surface of the pore is covered by a water layer for all systems. In addition to the interaction with water, an interaction of functional groups with the surface is observed which is shielded under hydration. Due to these interactions, the number of isolated groups and their stability is increased under the influence of the environment that reduces the proton transport mechanism which has been described before. Apart from the proton transport mechanism known from the vacuum system, two additional mechanisms occur under the chemical environment. These mechanism directly involve water molecules. One possibility is the complete deprotonation of the functional group, followed by water based proton transport as expected for acidic system, e.g. sulphonic acid. Another possibility is a water based proton transport over short distances from one proton conducting group to another. The three competing mechanisms are studied by free energy calculations and their occurance is evaluated according to the local environment conditions. The proton transport mechanisms involving water are more favourable in sulphonic acid functionalised particles, while the dominating mechanism is comparable to the mechanism in vacuum for imidazole system.