A Composite Anion Conducting Membrane Based on Quaternized Cellulose and Poly(Phenylene Oxide) for Alkaline Fuel Cell Applications

In this study, composite anion exchange membranes (AEMs) were synthesized by cross-linking poly(phenylene oxide) (PPO) with cellulose functionalized by 1,4-diazabicyclo[2.2.2]-octane (DABCO) or di-guanidine (DG). The structural and morphological characteristics of the synthesized AEMs were characterized by FTIR, 1H-NMR, SEM, TEM, and AFM, while their performance was evaluated in terms of ionic conductivity, water uptake, ion exchange capacity, and tensile strength with respect to the loading of the quaternized cellulose in the quaternized PPO (qPPO) matrix. The composite AEMs exhibited considerably enhanced mechanical and alkaline stability as well as good anion conductivity. The composite AEM with 7 wt% of cellulose functionalized with DG in the qPPO matrix (qPPO/DG-Cel7) exhibited a maximum hydroxide conductivity of 0.164 S cm−1. Furthermore, a urea/O2 fuel cell prepared using this composite membrane showed a maximum power density of 12.3 mW cm−2. The results indicated that the cellulose-based composite membranes showed a satisfactory performance in alkaline fuel cell applications.

Electrospun Anion-Conducting Ionomer Fibers—Effect of Humidity on Final Properties

Anion-conducting ionomer-based nanofibers mats are prepared by electrospinning (ES) technique. Depending on the relative humidity (RH) during the ES process (RHES), ionomer nanofibers with different morphologies are obtained. The effect of relative humidity on the ionomer nanofibers morphology, ionic conductivity, and water uptake (WU) is studied. A branching effect in the ES fibers found to occur mostly at RHES < 30% is discussed. The anion conductivity and WU of the ionomer electrospun mats prepared at the lowest RHES are found to be higher than in those prepared at higher RHES. This effect can be ascribed to the large diameter of the ionomer fibers, which have a higher WU. Understanding the effect of RH during the ES process on ionomer-based fibers’ properties is critical for the preparation of electrospun fiber mats for specific applications, such as electrochemical devices.

“Intrinsic” Anion Exchange Polymers through the Dissociation of Strong Basic Groups: PPO with Grafted Bicyclic Guanidines

We synthesized anion exchange polymers by a reaction of chloromethylated poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) with strongly basic 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). TBD contains secondary and tertiary amine groups in the guanidine portion. To favor the functionalization with the secondary amine, TBD was activated with butyl lithium. The yield of amine formation via the reaction of the benzyl chloride moiety with TBD was 85%. Furthermore, we prepared polymers with quaternary ammonium groups by the reaction of PPO-TBD with CH3I. The synthesis pathways and ionomer structure were investigated by NMR spectroscopy. The thermal decomposition of both ionomers, studied by thermogravimetry, started above 200 °C, corresponding to the loss of the basic group. The ion exchange capacities, water uptake and volumetric swelling are also reported. The “intrinsic” anion conductivity of PPO-TBD due to the dissociation of grafted TBD was in the order of 1 mS/cm (Cl form). The quaternized ionomer (PPO-TBD-Me) showed an even larger ionic conductivity, above 10 mS/cm at 80 °C in fully humidified conditions.