UV-Controlled Nitrene Crosslinking in Poly(phenylene oxide) Anion Exchange Membranes

Anion exchange membranes (AEMs) promise significant capital cost saving associated with enabling use of Pt-group-free electrodes and components in alkaline fuel cells and electrolyzer devices. However, AEMs often lack the chemical and mechanical stability required for widespread commercial adoption. Crosslinking has proven to be an effective method to permit increased ion exchange capacity (IEC) while preventing exponential water uptake and retaining both conductivity and mechanical strength. In this work, we leverage molecular dynamics simulations to explore crosslinking methodologies in silico. We present a reproducible and quantitative UV-based nitrene chemistry that utilizes a mobile crosslinker that is straightforward to synthesize and implement. This crosslinking strategy significantly mitigates excess water uptake and improves alkaline stability without sacrificing IEC during the cure process. Additionally, we characterize electrochemically fielded AEMs by small angle X-ray scattering, mechanical strength testing, and other post-mortem analyses. The operational lifetime of crosslinked AEMs prepared in this work is 5 times greater than corresponding untreated AEMs. This work is performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 within the LDRD program 21-ERD-013. LLNL-ABS-848147.