Ultra-thin proton conducting carrier layers for scalable integration of atomically thin 2D materials with proton exchange polymers for next-generation PEMs.

Scalable approaches for synthesis and integration of proton selective atomically thin 2D materials with proton conducting polymers can enable next-generation proton exchange membranes (PEMs) with minimal crossover of reactants or undesired species while maintaining adequately high proton conductance for practical applications. Here, we systematically investigate facile and scalable approaches to interface monolayer graphene synthesized via scalable chemical vapor deposition (CVD) on Cu foil with the most widely used proton exchange polymer Nafion 211 (N211, ∼25 μm thick film) via (i) spin-coating a ∼700 nm thin Nafion carrier layer to transfer graphene (spin + scoop), (ii) casting a Nafion film and cold pressing (cold press), and (iii) hot pressing (hot press) while minimizing micron-scale defects to <0.3% area. Interfacing CVD graphene on Cu with N211 via cold press or hot press and subsequent removal of Cu via etching results in ∼50% lower areal proton conductance compared to membranes fabricated via the spin + scoop method. Notably, the areal proton conductance can be recovered by soaking the hot and cold press membranes in 0.1 M HCl, without significant damage to graphene. We rationalize our finding by the significantly smaller reservoir for cation uptake from Cu etching for the ∼700 nm thin carrier Nafion layer used for spin + scoop transfer compared to the ∼25 μm thick N211 film for hot and cold pressing. Finally, we demonstrate performance in H 2 fuel cells with power densities of ∼0.23 W cm -2 and up to ∼41-54% reduction in H 2 crossover for the N211|G|N211 sandwich membranes compared to the control N211|N211 indicating potential for our approach in enabling advanced PEMs for fuel cells, redox-flow batteries, isotope separations and beyond.