Elucidating the Water and Methanol Dynamics in Sulfonated Polyether Ether Ketone Nanocomposite Membranes Bearing Layered Double Hydroxides

Abstract

Conventional Nafion membranes demonstrate a strong affinity for methanol, resulting in a high fuel crossover, poor mechanical stability, and thus poor performance in direct methanol fuel cells (DMFCs). This study involves the synthesis and physiochemical characterization of an alternative polymer electrolyte membrane for DMFCs based on sulfonated poly(ether ether ketone) and a layered double hydroxide (LDH) material. Nanocomposite membranes (sPL), with filler loading ranging between 1 wt% and 5 wt%, were prepared by simple solution intercalation and characterized by XRD, DMA, swelling tests, and EIS. For the first time, water and methanol mobility inside the hydrophilic channels of sPEEK-LDH membranes were characterized by NMR techniques. The introduction of LDH nanoplatelets improved the dimensional stability while having a detrimental effect on methanol mobility, with its self-diffusion coefficient almost two orders of magnitude lower than that of water. It is worth noting that anionic lamellae are directly involved in the proton transport mechanism, thus enabling the formation of highly interconnected paths for proton conduction. In this regard, sPL3 yielded a proton conductivity of 110 mS cm−1 at 120 °C and 90% RH, almost attaining the performance of the Nafion benchmark. The nanocomposite membrane also showed an excellent oxidative stability (over more than 24 h) during Fenton’s test at 80 °C. These preliminary results demonstrate that an sPL3 nanocomposite can be potentially and successfully applied in DMFCs.

Keywords

• direct methanol fuel cells
• sPEEK
• layered double hydroxides
• nanocomposite membranes
• PFG-NMR
• methanol crossover