Riccardo Narducci

Mixed Membrane Matrices Based on Nafion/UiO-66/SO3H-UiO-66 Nano-MOFs: Revealing the Effect of Crystal Size, Sulfonation, and Filler Loading on the Mechanical and Conductivity Properties

Mixed membrane matrices (MMMs) made up with Nafion and nanocrystals of zirconium metal-organic framework (MOF) UiO-66 or the analogous sulfonated SO3H-UiO-66 were prepared by varying the filler loading and the size of the crystals. The combined effects of size and loading, together with the presence of sulfonic groups covalently linked to the MOFs, were studied with regard to the conductivity and mechanical properties of the obtained composite matrices. A large screening of membranes was preliminarily made and, on the most promising samples, an accurate conductivity study at different relative humidities and temperatures was also carried out. The results showed that membranes containing large crystals (200 nm average size) in low amounts (around 2%) displayed the best results in terms of proton conductivity values, reaching values by 30% higher than those of pure Nafion, while leaving the mechanical properties substantially unchanged. On the contrary, MMMs containing MOFs of small size (20 nm average size) did not show any conductivity improvements if compared to pure Nafion membranes. The effect of MOF sulfonation was negligible at low filler loading whereas it became important at loading values around 10%. Finally, membranes with a high filler loading (up to 60 wt %) of sulfonated UiO-66 showed a slight reduction of conductivity in comparison with membranes loaded at 20% of nonsulfonated ones.

Stabilized sulfonated aromatic polymers by in situ solvothermal cross-linking

The cross-link reaction via sulfone bridges of sulfonated polyetheretherketone (SPEEK) by thermal treatment at 180 °C in presence of dimethylsulfoxide (DMSO) is discussed. The modifications of properties subsequent to the cross-linking are presented. The mechanical strength as well as the hydrolytic stability increased with the thermal treatment time, i.e., with the degree of cross-linking. The proton conductivity was determined as function of temperature, IEC, degree of cross-linking and hydration number. The memory effect, which is the membrane ability to “remember” the water uptake reached at high temperature also at lower temperature, is exploited in order to achieve high values of conductivity. Membranes swelled at 110 °C can reach a conductivity of 0.14 S/cm at 80°C with a hydration number () of 73.

How to improve Nafion with tailor made annealing

A tailor-made annealing procedure was developed for Nafion in order to avoid a critical degradation of the mechanical properties associated with a decrease of the ionic conductivity. The formation of layered morphologies, prevalently oriented in the direction parallel to the membrane surface, is responsible of the decay in fuel cell operation conditions. Nafion membranes are annealed at 140 °C over 7 days in the presence of dimethylsulfoxide (DMSO) as a proton-acceptor solvent. The important increase of mechanical stability is related to the formation of a crystalline phase, which acts as a physical cross-linker. The procedure is followed by hydrothermal annealing in liquid water in order to obtain an optimal water uptake at equilibrium (tailor made). To better understand the behavior of these polymers, we use the INCA method (Ionomer nc Analysis) and compare with dynamic mechanical analysis (DMA). The stabilized materials are proposed for use in intermediate temperature fuel cells, where the mechanical stabilization by the annealing procedure plays a fundamental role.