期刊
JOURNAL OF MATERIALS CHEMISTRY A
卷 9, 期 38, 页码 22025-22038出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta05166k
关键词
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资金
- UK's Engineering and Physical Sciences Research Council (EPSRC) [EP/R044163/1]
- EPSRC [EP/I004882/1]
- AFC Energy PLC (Dunsfold, Surrey)
- EPSRC [EP/M022749/1, EP/R044163/1, EP/I004882/1] Funding Source: UKRI
This study investigates the preparation process and issues of radiation-grafted anion-exchange membranes, finding that introducing diamine agents into the amination process is the most effective method for crosslinking in applications like RED cells.
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 '-tetramethylhexane-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.
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