DATASET (CC-BY): Radiation-grafted anion-exchange membranes for reverse electrodialysis: a comparison of N,N,N',N'-tetramethylhexene-1,6-diamine crosslinking (amination stage) and divinylbenzene crosslinking (grafting stage)

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Main article abstract:Radiation-grafted
anion-exchange membranes (RG-AEM) are being developed to evaluate a range of
chemistries that have relevance to a variety of electrochemical applications including
reverse electrodialysis (RED) salinity gradient power. RG-AEMs are typically
fabricated using an electron-beam activated (peroxidated) polymer substrate
film. These activated films are first grafted with a monomer, such as
vinylbenzyl chloride (VBC) and then reacted with a variety of tertiary amines
to yield the desired RG-AEMs. The amination process forms covalently bound quaternary
ammonium (QA) head-groups that allow the RG-AEMs to conduct anions such as Cl⁻.
RG-AEMs are of interest as they exhibit high conductivities (100 mS cm-1
at elevated temperatures when containing Cl⁻ anions). However, the current
generation of RG-AEMs have two main Achilles’ heels: (1) they exhibit low
permselectivities; and (2) they exhibit a high degree of swelling in water. Introducing
covalent crosslinking into ion-exchange membranes is a well-known strategy to
overcome these issues but it often comes with a price – a significantly lowered
conductivity (raised in situ resistance). Therefore, the level of
crosslinking must be carefully optimised. RG-AEMs can be primarily crosslinked
using two methods: (1) introduction of a divinyl monomer into the monomer
mixture used during grafting; or (2) introduction of a diamine agent into the
amination process. This study looks into both methods where either
divinylbenzene (DVB) is added into the grafting mixture or N,N,N',N'-tetramethylhexene-1,6-diamine
(TMHDA) is added into the amination mixture. We show
that on the balance of two application-relevant properties (resistances in
aqueous NaCl (0.5 mol dm-3) solution and permselectivity), the
diamine crosslinking method is the most effective for RG-AEMs being used in RED
cells.