[en] Highlights: • Ni/NiO anodes are processed by electrodeposition NiO from ionic liquids • Annealed Ni/NiO-electrode provides enhanced specific capacity and stable cyclability • NiO sub-layer, formed by thermal oxidation, is the main origin of capacity increase • Electrochemical performance of Ni/NiO anodes was evaluated in half and full cells - Abstract: An innovative route to obtain Ni/NiO core-shell foam-based anodes for lithium-ion batteries is presented. Commercial Ni foams are conformally coated with NiO by ionic liquid-based electrodeposition. The electrochemical behavior of the resulting Ni/NiO electrodes in half coin cells with lithium counter electrode is investigated. The results are qualitatively correlated to the microstructural properties, including effects of the thermal annealing at 500 °C, of the NiO shell. The formation a NiO sub-layer by the thermal oxidation of the Ni foam seems to play a crucial role in the enhanced performance of the annealed Ni/NiO anodes, which exhibit a reversible discharge capacity around 0.8 mAh/cm"2. Furthermore, the Ni/NiO core-shell foam-based anodes are evaluated in full coin Li-ion cells with high voltage LiMn_0_._8Fe_0_._2PO_4 cathode. Promising cyclability is reached in NiO-LMFP coin cells under cycling at 0.4C.

[en] Borosilicate german glass SG7 samples, obtained by frit sintering, were irradiated with different fluences of thermal neutrons in the nucleus of a nuclear reactor. The nuclear reaction ¹⁰ B(n,α)⁷ Li, where the ¹⁰ B isotope is one of the natural glass components, was used to generate alpha particles throughout the glass volume. The maximum alpha disintegration per unit volume achieved was equivalent to that accumulated in a borosilicate glass with nuclear wastes after 3.8 million years. Through Vickers indentations values for microhardness, stress for 50% fracture probability (Weibull statistics) and estimation of the toughness were obtained as a function of alpha radiation dose. Two counterbalanced effects were found: that due to the disorder created by the alpha particles in the glass and that due to the annealing during irradiation (temperature below 240 deg C). Considering the alpha radiation effect, glasses tend decrease Vickers hardness, and to increase thr 50% fracture probability stress with the dose increase. (author)

[en] Highlights: • Al, Si and Na are leached from the surface of the glass ionomer for common infusions. • The storage of the glass ionomer in mineral water causes the loss of F and Na. • K, Mn, Mg and Fe are incorporated into the ionomer surface from common infusions. • Ca and La increase their concentration modifying the density of the ionomer surface layer. • The modified surface layer is about 3 to 6 µm thick, depending on the immersion time. The effect of four commonly consumed beverages as mineral water, coffee, tea and mate tea on the elemental composition of a commercial glass ionomer was studied using Particle Induced X-ray Emission (PIXE) and Rutherford backscattering (RBS) techniques. We found that after immersion in acidic media, some elements as Al, Si and Na are lost from the glass-ionomer whereas others heavier, as K, Ca and La, increase their concentration at the surface. Although the concentration profiles of Al and Si are different in different media, in all of them the Al:Si ratio was close to unity and remained constant for different periods of immersion in all media. The incorporation of K, Mg and Fe to the surface is found for common infusions while for mineral water the glass-ionomer mainly loses F and Na.The RBS technique showed that immersion in different media produced a modification of the density of the glass ionomer surface layer due to the increment of the concentration of heavier elements at the surface. The thickness of the modified surface layer extends up to 3 µm when the immersion time is seven days and more than 6 µm after 33 days of immersion.

[en] Highlights: • Importance of mixing intensity for aqueous LiFePO₄ cathode slurries is demonstrated. • Fe³⁺ rich layer formation on intensively mixed LiFePO₄ electrode surface is detected. • C/LiFePO₄ pouch cells with aqueous processed electrodes show outstanding cyclability. • Aqueous cathode slurry processing is viable approach toward cheaper and greener LIBs. - Abstract: The positive electrodes based on nano- and micrometric carbon coated LiFePO₄ (LFP) powders are prepared via aqueous slurry processing using “normal” and “intensive” mixing procedures. The XRD, XPS, and electrochemical characterization reveal that the “intensive” mixing process improves the discharge C-rate capability of the n-LFP cathode however provokes formation of an undesirable thin surface layer enriched by Fe³⁺ species. The waterborne graphite anodes and LiFePO₄ cathodes for the energy and power cells are being developed, upscaled and manufactured on a pilot plant. Energy LiFePO₄/C pouch cells demonstrate outstanding durability maintaining 80% of initial discharge capacity (IDC) after 7450 and 2400 full cycles under 1D and 4D discharge currents, respectively. Moreover, further cycling of the energy cell working under 1C/4D protocol reveals its extra-long secondary life (70% of IDC on 9200^th cycle). Power LiFePO₄/C pouch cell shows long lasting cycle life retaining 80% of IDC after 3350 cycles under harsh cycling conditions (3C/8D). The reported results are being achieved despite confirmed water release from lithium iron phosphate cathodes to the electrolyte. Finally, viability of aqueous processing of the electrodes without sacrificing electrochemical performance of LiFePO₄/C batteries is clearly proven.

[en] The effect of the organic solvent polarity on the properties of unsupported PtRu catalyst inks and on the performance of the catalyst layers prepared with them for the methanol electrooxidation, has been studied. The light scattering results indicate that the PtRu-Nafion"® aggregates in the inks prepared with n-butyl acetate (NBA) are larger than those prepared with 2-propanol (IPA). The lower polarity of the former favours the aggregation of Nafion"® and nanoparticles. The electron microscopy images and porosimetry measurements of the catalyst layers show that the secondary pore volume between the agglomerates is larger for NBA. The linear sweep voltammetry and eis results for the methanol electrooxidation in the three-electrode cell denote the higher active surface area for NBA and comparable specific oxidation rates of the intermediates in both catalysts layers. The current densities for PtRu anode catalyst layers in single DMFC are higher when the solvent is NBA, the mass transport limitations being much more apparent with IPA. The adapted transmission line equivalent circuit to interpret the impedance results in single DMFC indicates that the proton resistance for NBA is significantly lower than for IPA, thus suggesting that the greater number of accessible active sites for methanol oxidation in the former are well connected to the Nafion"® ionomers and easier transported to the membrane.

[en] This fundamental study deals with the electrochemical stability of several non-conventional carbon based catalyst supports, intended for low temperature proton exchange membrane fuel cell (PEMFC) cathodes. Electrochemical surface oxidation of raw and functionalized carbon nanofibers, and carbon black for comparison, was studied following a potential step treatment at 25.0 deg. C in acid electrolyte, which mimics the operating conditions of low temperature PEMFCs. Surface oxidation was characterized using cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Cyclic voltammograms clearly showed the presence of the hydroquinone/quinone couple. Furthermore, identification of carbonyl, ether, hydroxyl and carboxyl surface functional groups were made by deconvolution of the XPS spectra. The relative increase in surface oxides on carbon nanofibers during the electrochemical oxidation treatment is significantly smaller than that on carbon black. This suggests that carbon nanofibers are more resistant to the electrochemical corrosion than carbon black under the experimental conditions used in this work. This behaviour could be attributed to the differences found in the microstructure of both kinds of carbons. According to these results, carbon nanofibers possess a high potential as catalyst support to increase the durability of catalysts used in low temperature PEMFC applications.

[en] NiO thin films have been successfully deposited by cathodic electrochemical deposition in N-butyl-N-methylpyrrolidinium bis(trifloromethanesulfonyl)imide room temperature ionic liquid (IL), giving an unambiguous proof of concept of the metal oxide electrodeposition in aprotic ILs without metal hydroxide formation as an intermediate phase. The electrochemical phenomena involved in the deposition process have been analyzed by cyclic voltammetry, pointing out that the electrochemical reduction of Ni²⁺ may be quenched in oxygenated IL electrolytes. The physico-chemical properties of the obtained NiO thin films have been characterized by electron scanning and atomic force microscopies, X-ray diffraction and Fourier transform infrared X-ray photo-electron spectroscopies. By taking advantage of the present electrodeposition route, ZnO/NiO heterostructures have been built. The current density-voltage characteristic of the resulting device exhibits clear rectifying behavior, with a rectification factor of 3 × 10³ at V = ±1 V. This result anticipates a significant potential of the present electrochemical route in the metal oxide electronics.

[en] The favoured mechanism of adsorption of dextran on the surface of maghemite nanoparticles (5 nm) prepared by laser pyrolysis seems to be the collective hydrogen bonding between dextran hydroxyl groups and iron oxide particle surface. After heating, the formation of a surface complex between the polysaccharide oxygen atoms and the surface iron atoms gave rise to a stronger bonding

[en] Highlights: ► Novel electrochemical deposition of NiO from NO₃⁻ reduction in ionic liquids. ► Evidence of need of aprotic media for the single-step cathodic deposition of NiO. ► Remarkable advantages of novel PYR14NO₃ salt vs. O₂ and (Na,K)NO₃. ► Nanowire array architecture-based ZnO/NiO n–p diodes. -- Abstract: Aprotic PYR14TFSI (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)) ionic liquid served to develop a new electrochemical route for one-step deposition of NiO from PYR14NO₃ reduction (1-butyl-1-methylpyrrolidinium nitrate) in a Ni(TFSI)₂ (Nickel (II) bis(trifluoromethanesulfonyl)imide) containing electrolyte. The high solubility of the novel PYR14NO₃ salt in PYR14TFSI (>0.1 M) in comparison with other oxygenated precursors such as oxygen gas, NaNO₃ or KNO₃ (i.e. 10–15 mM) allows the formulation of a broad variety of electrolytes which opens wide possibilities to tune the physico-chemical properties of NiO films (e.g. morphology: from flat to nanostructured films). Furthermore, electrochemical deposition in an electrolyte containing low water concentration (>30 ppm by Karl Fisher titration) served to demonstrate that only a small amount of moisture dramatically affects the electrochemical reduction of NO₃⁻, resulting in OH⁻ generation close to the cathode and subsequent NiO(OH)/Ni(OH)₂ deposition, as proved by X-ray diffraction and X-ray photoelectron spectroscopy. This finding highlights the importance of aprotic ionic liquids in developing a general electrochemical route for metal oxide deposition without the formation of metal hydroxide species, thus avoiding the requirement for post-deposition annealing treatments. The versatility of the present deposition route as well as its impact in (opto)electronic devices was pointed out by the successful preparation of nanostructured n–p ZnO/NiO heterojunctions exhibiting rectifying current–voltage characteristics

[en] Biocompatible magnetic dispersions have been prepared from γ-Fe₂O₃ nanoparticles (5 nm) synthesized by continuous laser pyrolysis of Fe(CO)₅ vapours. The feasibility of using these dispersions as magnetic resonance imaging (MRI) contrast agents has been analysed in terms of chemical structure, magnetic properties, ¹H NMR relaxation times and biokinetics. The magnetic nanoparticles were dispersed in a strong alkaline solution in the presence of dextran, yielding stable colloids in a single step. The dispersions consist of particle-aggregates 25 nm in diameter measured using transmission electron microscope and a hydrodynamic diameter of 42 nm measured using photon correlation spectroscopy. The magnetic and relaxometric properties of the dispersions were of the same order of magnitude as those of commercial contrast agents produced using coprecipitation. However, these dispersions, when injected intravenously in rats at standard doses showed a mono-exponential blood clearance instead of a biexponential one, with a blood half-life of 7 ± 1 min. Furthermore, an important enhancement of the image contrast was observed after the injection, mainly located at the liver and the spleen of the rat. In conclusion, the laser pyrolysis technique seems to be a good alternative to the coprecipitation method for producing MRI contrast agents, with the advantage of being a continuous synthesis method that leads to very uniform particles capable of being dispersed and therefore transformed in a biocompatible magnetic liquid