The Latest Developments in Radiation-Grafted Anion-Exchange Polymer Electrolytes for Low Temperature Electrochemical Systems
Authors: Varcoe John , Bance-Souahli Rachida , Chakraborty Arup , Choolaei Mehdi , Crean Carol , Giron Rodriguez Carlos , Óladóttir Joensen Bjørt , Lee Judy , Periasamy Arun Prakash , Salam Ihtasham , Seger Brian , Whelligan Daniel , Willson Terrence 
Published: July 2022

Anion-exchange membranes (AEM) are being developed for use in electrochemical technologies including fuel cells (AEMFC),water electrolysis (AEMWE for green hydrogen), electrolysers for CO2 reduction (CO2RR), and reverse electrodialysis (RED). Radiation-grafted AEMs (RG-AEM) represent a promising class of AEM that can exhibit high conductivities (OH- conductivities of > 200 mS cm-1 at temperatures above 60 °C) and favourable in situ water transport characteristics). Hence, RG-AEMs have shown significant promise when tested in AEMFCs alongside powdered radiation-grafted anion-exchange ionomers (RG-AEI), producing high performances and promising durabilities [Energy Environ. Sci., 12, 1575 (2019) and Nature Commun., 11, 3561 (2020)], even at temperatures above 100 °C [Dekel et al., J. Power Sources Adv., 5, 100023 (2020)].
An Achilles heel with RG-AEM types is that they can swell excessively in water and have large dimensional changes between the dehydrated and hydrated states. This limits the ion-exchange capacities (IEC) that can be used: excessive IECs in RG-AEM will cause excessive swelling and poorer robustness. This clearly indicates that additional crosslinking is needed. As Kohl et al. have highlighted, optimised crosslinking can lead to production of high-IEC AEMs that are both robust enough to be < 20 µm in thickness and also low swelling [e.g. J. Electrochem. Soc., 166, F637 (2019)], allowing truly world-leading AEMFC performances.
RG-AEMs are also being used as a screening platform for down-selecting different (cationic) head-group chemistries for use in RED cells (a salinity gradient power technology), where different head-groups may lead to different AEM characteristics such as: in-cell resistance (when in contact with aqueous electrolytes), permselectivity, and fouling characteristics (when real world waters such as industrial brines, seawater and freshwater are used). It was evident very early on in these studies that RG-AEMs (desirably) exhibit extremely low resistances but also (undesirably) very low permselectivities when un-crosslinked (less than the required 90%+ permselectivity). Our work on RG-type cation-exchange membranes [Sustainable Energy Fuels, 3, 1682 (2019)] clearly shows that introduction of crosslinking can improve permselectivity.
Crosslinking always involves a compromise, where its introduction can improve a membrane characteristic (e.g. reduced swelling or improved permselectivity) but also leads to lower conductivities or poorer transport of chemical species through the membranes. Hence, crosslinking types and levels need to be carefully controlled. With RG-AEMs (made by electron-beam activation (peroxidation) of inert polymer films, followed by grafting of monomers and post-graft amination), we have a choice of introducing crosslinking at various stages. The figure below summarises the two different approaches to crosslinking that will be discussed in the presentation: adding a divinyl-type crosslinker into the grafting mixture or adding a diamine-type crosslinker into the amination step.
This presentation will present a selection of recent RG-AEM and RG-AEI developments from a number of projects:
(1) REDAEM: AEMs for RED cells [EPSRC Grant EP/R044163/1];
(2) CARAEM: Novel RG-AEMs for AEMFCs and AEMWE [EPSRC Grant EP/T009233/1];
(3) SELECTCO2: RG-AEMs being tested in CO2RR cells [EU Horizon 2020 grant agreement 851441].
This presentation will show:
(a) RG-AEMs made from thin high density polyethylene (HDPE) precursors appear better for application in AEMFCs, while RG-AEMs from made from thicker ETFE precursors appear to be better for CO2RR cells and RED;
(b) RG-AEMs can be made using a variety of crosslinking strategies;
(c) RG-AEIs can be made using ETFE powders and give optimal performance after cryogrinding down to micrometer sizes;

Figure 1