Polymer electrolyte membrane fuel cells (PEMFCs) continue to receive extensive attention because of their utility as a clean energy source for automotive, stationary, and portable applications.[1] The proton conductivity of the polymer electrolyte membrane (PEM) is one of the key factors limiting the performance of PEMFCs, which depends on the relative humidity, and controls the cost and durability. [2] Consequently, an improvement in the proton conductivity of the electrolyte membrane even by an order of magnitude could change the performance of fuel cells dramatically. [3] Currently, Nafion-based membranes are widely used as the PEM in fuel cells that operate from 60 to 80 8C. Although these membranes show good proton conductivities from 0.1 to 0.01 S cm À1 in a humid environment, they have many limitations, such as: 1) dependence on water for conductivity; 2) high methanol permeability; 3) a tendency to disintegrate in the presence of hydroxyl radicals, an intermediate in the cathode reaction; and 4) moderate mechanical and chemical stability.To improve the performance of electrolytes used in PEMFCs, two different approaches have been adopted. First is the synthesis of alternative membranes that could operate at higher temperatures without the need for humidification. The phosphoric acid doped polybenzimidazole membrane is a widely exploited example in this category. [4,5]
Development of chemically stable proton conductors for solid oxide fuel cells (SOFCs) will solve several issues, including cost associated with expensive inter-connectors, and long-term durability. Best known Y-doped BaCeO3 (YBC) proton conductors-based SOFCs suffer from chemical stability under SOFC by-products including CO2 and H2O. Here, for the first time, we report novel perovskite-type Ba0.5Sr0.5Ce0.6Zr0.2Gd0.1Y0.1O3−δ by substituting Sr for Ba and co-substituting Gd + Zr for Ce in YBC that showed excellent chemical stability under SOFC by-products (e.g., CO2 and H2O) and retained a high proton conductivity, key properties which were lacking since the discovery of YBCs. In situ and ex- situ powder X-ray diffraction and thermo-gravimetric analysis demonstrate superior structural stability of investigated perovskite under SOFC by-products. The electrical measurements reveal pure proton conductivity, as confirmed by an open circuit potential of 1.15 V for H2-air cell at 700°C, and merits as electrolyte for H-SOFCs.
The application of sulfonic acid-functionalized multiwalled (s-MWNT) carbon nanotubes to manipulate the hydrophilic domain size of Nafion membranes is explored here as an option for tuning the proton conductivity of polymer electrolyte membranes for hydrogen-oxygen fuel cells. The electrochemical impedance experiments provide preliminary evidence of increased proton conductivity, while small-angle X-ray scattering measurements line out enhanced ionic cluster domain size in these composite membranes as the central reason for higher conductivity (70 A for the optimum composite membrane vs 50 A for Nafion 115) values. Scanning electrochemical microscopy indicates synergistic interaction between the sulfonic acid functional groups present in the Nafion membrane and those on the nanotube surface. More interestingly, the nanotube-tailored Nafion membranes ameliorate the performance of fuel cells as confirmed by measurements at a single-cell level, which reveal a maximum power density of 380 mW cm(-2), higher than those of Nafion 115 (250 mW cm(-2)) and recast Nafion (230 mW cm(-2)) membranes. Thus, in addition to providing an elegant means of controlling the ionic cluster size, the strategic approach of using CNT both as an anchoring backbone for -SO(3)H groups to enrich proton conductivity and as a blending agent to improve the mechanical characteristics of the Nafion phase might be helpful in alleviating many critical problems associated with the use of commercial Nafion membranes.
The ability of phosphonated carbon nanotubes to offer an unprecedented approach to tune both proton conductivity and mechanical stability of hybrid polymer electrolytes based on the polybenzimidazole membrane is demonstrated for fuel cell applications. The covalent attachment between the amino group of the 2-aminoethylphosphonic acid precursor and CNTs has been confirmed by NMR and IR experiments, while EDAX analysis indicates that one out of every 20 carbon atoms in the CNT is functionalized. Proton conductivity of the composite membrane shows a remarkable 50% improvement in performance, while a maximum power density of 780 and 600 mW cm−2 is obtained for the composite and pristine membranes, respectively. Finally, the ultimate strength determined for the composite and pristine membranes is 100 and 65 MPa, respectively, demonstrating the superiority of the composite. This study opens up a new strategy to systematically tune the properties of polymer electrolytes for special applications by using appropriately functionalized CNTs.
We demonstrate a facile construction of iron nitride-doped carbon nanofiber by effectively utilizing the existing slit pores and rough edges along the inner wall of the substrate as originated by virtue of its cup-stack structure for effectively increasing the number of active sites and consequently the oxygen reduction activity.
We here demonstrate a remarkable potential-dependent morphological evolution of platinum mesostructures in the form of multipods, discs, and hexagons using a porous anodic alumina membrane (PAAM). These structures prepared potentiostatically at -0.7, -0.5 and -0.3 V, respectively, reveal unique shape-dependent electrocatalytic activity toward both formic acid and ethanol oxidation reactions. A comparison of the electrooxidation kinetics of these structures illustrates that hexagons show better performance toward formic acid oxidation whereas, for ethanol oxidation, multipods show significantly enhanced activity. Interestingly, the enhancement factor (R) for these mesostructures with respect to that of commercial platinized carbon toward formic acid oxidation ranges up to 2000% for hexagons whereas for multipods and disc they are about 700% and 300%, respectively. Similarly, for ethanol oxidation, the calculated value of R varies up to 600% for multipods while for disc and hexagons these values are 500% and 200%, respectively. These shape-dependent electrocatalytic activity of Pt mesostructures have been further correlated with XRD results. Thus, the present results demonstrate the importance of precise control of morphology by an electric field and their potential benefits especially for fuel cell applications since designing a better electrocatalyst for many fuel cell reactions continues to be an important challenge.
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