ABSTRACT
Anion exchange membranes (AEMs) are the heart of alkaline fuel cells and water electrolysis, and have made a great progress in recent years. However, AEMs are still unable to satisfy the needs of high conductivity and stability, hindering their widespread commercialization. Side chain regulations have been widely used to prepare highly conductive and durable AEMs. Here, we construct a series of polyaromatic AEMs grafted with fluorinated cation side chains and cation-free alkyl chains with different end groups to explore the polar discrimination of side chains on membrane performance. This work demonstrates that AEMs grafting the cation side chains with superhydrophobic fluorine pendent and alkyl side chains with hydrophilic pendent enhance water content and ion conductivity. This is due to the strong immiscibility between the hydrophilic and hydrophobic head groups which promotes the establishments of microphase separation and ion highways. Specifically, poly(binaphthyl-co-terphenyl piperidinium) containing fluorinated piperidinium side chains and alkyl chains with methoxy pendent (QBNTP-QFM) possesses a satisficed OH- conductivity (170.6 mS cm-1 at 80 °C) and can tolerate 5 M hot NaOH for 2100 h with only 3.4 % conductivity loss. Expectedly, the single cell with QBNTP-QFM yields a prominent maximum power density of 1.62 W cm-2 and the water electrolysis cell with QBNTP-QFM achieves a pronounced current density of 3.0 A cm-2 at 1.8 V, both cells also display a prominent durability for 120 h operation. The results prove that this side chain optimization can improve ion conductivity and is a promising method for AEM development.
ABSTRACT
In order to realise high ionic conductivity and improved chemical stability, a series of anion exchange membranes (AEMs) with semi-interpenetrating polymer network (sIPN) has been prepared via the incorporation of crosslinked poly(biphenyl N-methylpiperidine) (PBP) and spirobisindane-based intrinsically microporous poly(ether ketone) (PEK-SBI). The formation of phase separated structures as a result of the incompatibility between the hydrophilic PBP network and the hydrophobic PEK-SBI segment, has successfully promoted the hydroxide ion conductivity of AEMs. A swelling ratio (SR) as low as 12.2 % at 80 °C was recorded for the sIPN containing hydrophobic PEK-SBI as the linear polymer and crosslinked structure with a mass ratio of PBP to PEK-SBI of 90/10 (sIPN-90/10(PEK-SBI)). The sIPN-90/10(PEK-SBI) AEM achieved the highest hydroxide ion conductivity of 122.4 mS cm-1 at 80 °C and a recorded ion exchange capacity (IEC) of 2.26 meq g-1. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) clearly revealed the improved phase separation structure of sIPN-90/10(PEK-SBI). N2 adsorption isotherm indicated that the Brunauer-Emmett-Teller (BET) surface area of the AEMs increased with the increase of microporous PEK-SBI content. Interestingly, the sIPN-90/10(PEK-SBI) AEM showed good alkaline stability for being able to maintain a conductivity of 94.7 % despite being soaked in a 1 M sodium hydroxide solution at 80 °C for 30 days. Meanwhile, a peak power density of 481 mW cm-2 can be achieved by the hydrogen/oxygen single cell using sIPN-90/10(PEK-SBI) as the AEM.