The morphological changes of Si nanowires (Si NWs) cycled in 1:1 ethylene–carbonate (EC)/diethyl–carbonate (DEC) with or without different additives, fluoroethylene carbonate (FEC) or vinylene carbonate (VC), as well as the composition of the deposited solid–electrolyte interphase layer, are investigated by a combination of experimental microscopic and spectroscopic techniques. Scanning electron microscopy and optical spectroscopy highlight that the NW morphology is better preserved in samples cycled in the presence of FEC and VC additives compared to the additive-free electrolyte. However, only the use of FEC is capable of slightly mitigating the amorphization of silicon upon cycling. The solid electrolyte interphase (SEI) formed over the Si NWs cycled in the additive-free electrolyte is richer in organic and inorganic carbonates compared to the SEI grown in the presence of the VC and FEC additives. Furthermore, both additives are able to remarkably limit the degradation of the LiPF6 salt. Overall, the use of the FEC-additive in the carbonate-based electrolyte promotes both morphological and structural resilience of the Si NWs upon cycling thanks to the optimal composition of the SEI layer.
The Front Cover shows a schematic representation of the oxygen reduction reaction on our gas diffusion electrode. The composite catalyst is based on Pt/C and non‐stoichiometric CeO2. The high hygroscopicity of the latter plays a crucial role in optimizing the water drainage and the cathode/Nafion interface, resulting in a considerable improvement in proton conductivity and Fuel Cell performances. Cover design by Nicholas Carboni. More information can be found in the Research Article by L. Mazzapioda et al.
The design of highly efficient promoters for the oxygen reduction reaction (ORR) is an important challenge in the largescale distribution of proton exchange membrane (PEM) fuel cells. Hygroscopic cerium oxide (CeO 2 ) is here proposed as cocatalyst in combination with Pt. Physical chemical characterizations, by means of X-ray diffraction, vibrational spectroscopy, morphological and thermal analyses, were carried out, demonstrating high water affinity of the synthesized CeO 2 nanoparticles. Composite catalysts (i. e., Pt : CeO 2 1 : 0.5 and 1 : 1 wt: wt), were studied by either rotating disk electrode (RDE) and fuel cell tests performed at 80 °C and 110 °C. Interestingly, the cell adopting the Pt : CeO 2 1 : 0.5 catalyst enabled the achievement of high power densities reaching ~80 and ~35 mW cm À 2 under low relative humidity and high temperatures. This result demonstrates that tuning material surface properties (e. g. oxygen vacancies) could significantly boost the electrochemical performance of cathodes as a combined result of optimized water retention and improved ORR kinetic.
Vanadium can store large quantities of hydrogen (about 4 mass%). However, only half of it can be reversibly absorbed. To avoid this issue, various partial substitutions were previously proposed, such as Ni. In this work, we explore the synthesis of a V85Ni15 alloy by means of ball milling, a simpler and more scalable method compared to arc or induction melting usually applied for metal alloys. After ball milling the powders of the pure metals for 15 h in argon, SEM–EDX measurements confirmed the stoichiometry of the synthesized material, which has a typical particle dimension of the order of a few microns and is composed from the coalescence of nanometric primary particles. XRD indicated a BCC crystalline structure with a typical grain size of ≈3 nm. Hydrogen can be absorbed without activation procedures at high temperatures. Up to H/M ≈ 0.08, one can observe the occurrence of a solid solution of hydrogen in the alloy, while at a higher hydrogen content, the formation of a hydride is likely to occur. The maximum hydrogen content is H/M ≈ 0.4 at the maximum investigated pressure in this study of p ≈ 45 bar. Both the hydrogenation enthalpy and entropy decrease as the hydrogen content increases, and the shape of the sorption isotherms is different from that of V85Ni15 produced by induction melting, possibly because of the nanometric dimensions of the particles produced by ball milling.
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