Decoupling polymer, water and ion transport dynamics in ion-selective membranes for fuel cell applications

Ion conducting polymer membranes are designed for applications ranging from separation and dialysis, to energy conversion and storage technologies. A key application is in fuel cells, where the semi-permeable polymer membrane plays several roles. In a fuel cell, electrical power is generated from the electrochemical reaction between oxygen and hydrogen, catalysed by metal nanoparticles at the cathode and anode sites. The polymer membrane permits the selective transport of H+ or OH- to enable completion of the electrode half-reactions, plays a major role in the management of water that is necessary for the conduction process and is a product in the reactions, and provides a physical barrier against leakage across the cell. All of these functions must be optimised to enable high conduction efficiency under operational conditions, including high temperatures and aggressive chemical environments, while ensuring a long lifetime of the fuel cell. Polymer electrolyte membranes used in current devices only partially meet these stringent requirements, with ongoing research to assess and develop improved membranes for a more efficient operation and to help realise the transition to a hydrogen-fuelled energy economy. A key fundamental issue to achieving these goals is the need to understand and control the nature of the strongly coupled dynamical processes involving the polymer, water and ions, and their relationship to the conductivity, as a function of temperature and other environmental conditions. This can be achieved by using techniques that give access to information across a wide range of timescales. Given the complexity of the dynamical map in these systems, unravelling and disentangling the various processes involved can be accessed by applying the "serial decoupling" approach introduced by Angell and co-workers for ion-conducting glasses and polymers. Here we introduce this concept and propose how it can be applied to proton- and anion-conducting fuel cell membranes using two main classes of these materials as examples.