Aliphatic Anion Exchange Ionomers with Long Spacers and No Ether Links by Ziegler–Natta Polymerization: Properties and Alkaline Stability

In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler–Natta method, employing the complex ZrCl4 (THF)2 as a catalyst. A certain degree of crosslinking with N,N,N′,N′-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2 M KOH at 80 °C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a SN2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 °C. The ionic conductivity at 25 °C in the OH− form was 29.5 mS/cm.

Investigating the suitability of poly tetraarylphosphonium based anion exchange membranes for electrochemical applications

Anion exchange membranes (AEMs) are becoming increasingly common in electrochemical energy conversion and storage systems around the world (EES). Proton-/cation-exchange membranes (which conduct positive charged ions such as H+ or Na+) have historically been used in many devices such as fuel cells, electrolysers, and redox flow batteries. High capital costs and the use of noble metal catalysts are two of the current major disadvantages of polymer electrolyte membrane (PEM)-based systems. AEMs may be able to overcome the limitations of conventional PEMs. As a result, polymers with anion exchange properties have recently attracted a lot of attention due to their significant benefits in terms of transitioning from a highly acidic to an alkaline environment, high kinetics for oxygen reduction and fuel oxidation in an alkaline environment, and lower cost due to the use of non-precious metals. The aim of this research was to learn more about the development of a new AEM based on poly tetraarylphosphonium ionomers (pTAP), which has high ionic conductivity, alkaline stability, thermal stability, and good mechanical properties, making it a more cost-effective and stable alternative to conventional and commercial AEMs. A simple solution casting method was used to build novel anion exchange composite membranes with controlled thicknesses using the synthesized pTAP with polysulfone (PS). To ensure their suitability for use as an electrolyte in alkaline electrochemical systems, the composite membranes were characterized using FTIR, XRD, water uptake, ionic conductivity, and alkaline stability. At 40 °C, the PS/pTAP 40/60 percent membrane had a maximum ionic conductivity of 4.2 mS/cm. The thermal and mechanical stability of the composite membranes were also examined, with no substantial weight loss observed up to 150 °C. These findings pave the way for these membranes to be used in a wide variety of electrochemical applications.