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polymers Article Polymer Electrolyte Membranes Based on Nafion and a Superacidic Inorganic Additive for Fuel Cell Applications Lucia Mazzapioda, Stefania Panero and Maria Assunta Navarra * Department of Chemistry, Sapienza University of Rome. Piazzale Aldo Moro 5, 00185 Rome, Italy; lucia.mazzapioda@uniroma1.it (L.M.); stefania.panero@uniroma1.it (S.P.) * Correspondence: mariassunta.navarra@uniroma1.it; Tel.: +39-06-4991-3658 Received: 22 March 2019; Accepted: 5 May 2019; Published: 22 May 2019 Abstract: Nafion composite membranes, containing different amounts of mesoporous sulfated titanium oxide (TiO2-SO4) were prepared by solvent-casting and tested in proton exchange membrane fuel cells (PEMFCs), operating at very low humidification levels. The TiO2-SO4 additive was originally synthesized by a sol-gel method and characterized through x-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and ion exchange capacity (IEC). Peculiar properties of the composite membranes, such as the thermal transitions and ion exchange capacity, were investigated and here discussed. When used as an electrolyte in the fuel cell, the composite membrane guaranteed an improvement with respect to bare Nafion systems at 30% relative humidity and 110 ◦C, exhibiting higher power and current densities. Keywords: mesoporous sulfated titania; nanocomposite polymer electrolytes; PEM fuel cells 1. Introduction Fuel cells are electrochemical devices with high-energy conversion efficiency, minimized pollutant emission and other advanced features. Among the different types of fuel cells, including alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), direct-methanol fuel cell (DMFC), molten carbonate fuel cell (MCFC) and solid oxide fuel cell (SOFC), the proton exchange membrane fuel cell (PEMFC) is attractive both for automobile and stationary applications [1,2]. The conventional design of PEMFCs consists of anodic and cathodic compartments, separated by a proton exchange membrane. The most used as a proton exchange membrane for these devices is Nafion (Du Pont), a perfluorosulfonic acid polymer [3], thanks to its high proton conductivity, suitable mechanical properties, chemical and electrochemical stability, low fuel permeability and electronic insulation [4,5]. The major issue for this membrane is the decrease of its conductivity under desirable operating conditions, i.e., low relative humidity (RH) and temperature higher than 80 ◦C [6,7]. Indeed, on one hand, the electrode kinetics will be enhanced and the overpotential will be reduced when the temperature is increased. On the other side, at low RH the water management will be simpler with respect to devices working fully humidified [8]. According to several studies [9,10], a strategy to overcome these limits is to modify the polymer matrix with inorganic additives, that are able to improve the low RH and high temperature performances of PEMFCs [11,12]. These additives may be metal oxide nanoparticles, such as SiO2, TiO2, ZrO2 or functionalized inorganic materials, such as sulfated metal oxides [13,14]. The presence of acidic hygroscopic additives ensures better hydration and proton conductivity of the membranes, allowing working at the targeted conditions described above [15,16]. These composite membranes also decrease the cross-over of the gases during fuel cell operations [17]. Polymers 2019, 11, 914; doi:10.3390/polym11050914 www.mdpi.com/journal/polymersPDF Image | Polymer Electrolyte Membranes Based on Nafion Fuel Cell
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