Electrochemical Response of 3D-Printed Free-Standing Reduced Graphene Oxide Electrode for Sodium Ion Batteries Using a Three-Electrode Glass Cell.

Graphene and its derivatives have been widely used to develop novel materials with applications in energy storage. Among them, reduced graphene oxide has shown great potential for more efficient storage of Na ions and is a current target in the design of electrodes for environmentally friendly Na ion batteries. The search for more sustainable and versatile manufacturing processes also motivates research into additive manufacturing electrodes. Here, the electrochemical responses of porous 3D-printed free-standing log-type structures fabricated using direct ink writing (DIW) with a graphene oxide (GO) gel ink are investigated after thermal reduction in a three-electrode cell configuration. The structures delivered capacities in the range of 50-80 mAh g-1 and showed high stability for more than 100 cycles. The reaction with the electrolyte/solvent system, which caused an initial capacity drop, was evidenced by the nucleation of various Na carbonates and Na2O. The incorporation of Na into the filaments of the structure was verified with transmission electron microscopy and Raman spectroscopy. This work is a proof of concept that structured reduced GO electrodes for Na ion batteries can be achieved from a simple, aqueous GO ink through DIW and that there is scope for improving their performance and capacity.

New Insights on the Conversion Reaction Mechanism in Metal Oxide Electrodes for Sodium-Ion Batteries.

Due to the abundance and low cost of exchanged metal, sodium-ion batteries have attracted increasing research attention for the massive energy storage associated with renewable energy sources. Nickel oxide (NiO) thin films have been prepared by magnetron sputtering (MS) deposition under an oblique angle configuration (OAD) and used as electrodes for Na-ion batteries. A systematic chemical, structural and electrochemical analysis of this electrode has been carried out. The electrochemical characterization by galvanostatic charge-discharge cycling and cyclic voltammetry has revealed a certain loss of performance after the initial cycling of the battery. The conversion reaction of NiO with sodium ions during the discharge process to generate sodium oxide and Ni metal has been confirmed by X-ray photoelectron spectra (XPS) and micro-Raman analysis. Likewise, it has been determined that the charging process is not totally reversible, causing a reduction in battery capacity.

Sol-Gel Synthesis of Nanocrystalline Mesoporous Li4Ti5O12 Thin-Films as Anodes for Li-Ion Microbatteries.

The development of anodes based on Li4Ti5O12 (LTO) for lithium ion batteries has become very important in recent years on the basis that it allows a long service life (stability in charge-discharge cycling) and safety improvements. The processing of this material in the form of thin film allows for greater control of its characteristics and an improvement of its disadvantages, namely reduced electrical conductivity and low diffusion of lithium ions. In this work, we try to limit these disadvantages through the synthesis of a mesostructured carbon-doped Li4Ti5O12 thin-film with a pure spinel phase using a combination of a block-copolymer template and in situ synthesis of Li-Ti double alkoxide. Structural and electrochemical characterization has been carried out to determine the best conditions (temperature, time, atmosphere) for the thermal treatment of the material to reach a compromise between crystallinity and porosity distribution (pore size, pore volume, and interconnectivity).

Blend Hybrid Solid Electrolytes Based on LiTFSI Doped Silica-Polyethylene Oxide for Lithium-Ion Batteries.

Organic/inorganic hybrid membranes that are based on GTT (GPTMS-TMES-TPTE) system while using 3-Glycidoxypropyl-trimethoxysilane (GPTMS), Trimethyletoxisilane (TMES), and Trimethylolpropane triglycidyl ether (TPTE) as precursors have been obtained while using a combination of organic polymerization and sol-gel synthesis to be used as electrolytes in Li-ion batteries. Self-supported materials and thin-films solid hybrid electrolytes that were doped with Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared. The hybrid network is based on highly cross-linked structures with high ionic conductivity. The dependency of the crosslinked hybrid structure and polymerization grade on ionic conductivity is studied. Ionic conductivity depends on triepoxy precursor (TPTE) and the accessibility of Li ions in the organic network, reaching a maximum ionic conductivity of 1.3 × 10-4 and 1.4 × 10-3 S cm-1 at room temperature and 60 °C, respectively. A wide electrochemical stability window in the range of 1.5-5 V facilitates its use as solid electrolytes in next-generation of Li-ion batteries.

Transparent Sol-Gel Oxyfluoride Glass-Ceramics with High Crystalline Fraction and Study of RE Incorporation.

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO2-20LaF3 doped with Er3+ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 µm were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF3 crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF3 nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er3+ ions are preferentially embedded in the low phonon-energy LaF3 nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF3 nanocrystals. The effective concentration of rare-earth ions in the LaF3 nanocrystals is also estimated by X-ray absorption spectroscopy.

Consolidated Melting Gel Coatings on AZ31 Magnesium Alloy with Excellent Corrosion Resistance in NaCl Solutions: An Interface Study.

Magnesium alloys, with a density two-thirds that of aluminum, are very attractive for the industry. However, these alloys are extremely susceptible to corrosion in the presence of aggressive electrolytes such as NaCl solutions. Here, we designed hybrid coatings obtained by the consolidation of organically modified polysilsesquioxanes called "melting gels" for the corrosion protection of AZ31 magnesium alloy in NaCl solutions. The main focus was to study the interaction between coatings and substrate and the influence of the coating thickness on the final properties. Micro-scratch tests, adhesion by tape tests, confocal Raman microscopy, SEM-EDS, and ToF-SIMS indicate good adhesion of coatings based on the interaction of melting gels and substrate. These measurements indicate the presence of the Si-O-Mg bonds between the substrate and coatings. Electrochemical results show very low current densities (10-13 A cm-2) without any breakdown potential and impedance values of 1010 Ω cm2.

Transparent Glass-Ceramics Produced by Sol-Gel: A Suitable Alternative for Photonic Materials.

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF4 glass-ceramics. Moreover, a new SiO2 precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications.

29Si NMR and SAXS investigation of the hybrid organic-inorganic glasses obtained by consolidation of the melting gels.

This study is focused on structural characterization of hybrid glasses obtained by consolidation of melting gels. The melting gels were prepared in molar ratios of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) of 75%MTES-25%DMDES and 65%MTES-35%DMDES. Following consolidation, the hybrid glasses were characterized using Raman, 29Si and 13C Nuclear Magnetic Resonance (NMR) spectroscopies, synchrotron Small Angle X-Ray Scattering (SAXS) and scanning electron microscopy (SEM). Raman spectroscopy revealed the presence of Si-C bonds in the hybrid glasses and 8-membered ring structures in the Si-O-Si network. Qualitative NMR spectroscopy identified the main molecular species, while quantitative NMR data showed that the ratio of trimers (T) to dimers (D) varied between 4.6 and 3.8. Two-dimensional 29Si NMR data were used to identify two distinct types of T3 environments. SAXS data showed that the glasses are homogeneous across the nm to micrometer length scales. The scattering cross section was one thousand times lower than what is expected when phase separation occurs. The SEM images show a uniform surface without defects, in agreement with the SAXS results, which further supports that the hybrid glasses are nonporous.

Choosing the best molecular precursor to prepare Li4Ti5O12 by the sol-gel method using (1)H NMR: evidence of [Ti3(OEt)13](-) in solution.

(1)H NMR spectroscopy at 400 MHz in toluene-d8 of evaporated mixtures of lithium ethoxide and titanium(iv) isopropoxide in ethanol, used to prepare the spinel Li4Ti5O12 by the sol-gel method, may help clarify why the atomic ratio 5Li : 5Ti and not 4Li : 5Ti is the right choice to obtain the pure phase when performing hydrolysis at room temperature. The mixtures xLiOEt/yTi(OPr(i))4 in ethanol undergo alcohol exchange at room temperature, and the evaporated residues contain double lithium-titanium ethoxide [LiTi3(OEt)13] rather than simple mixtures of single metal alkoxides; this is of great relevance to truly understanding the chemistry and structural changes in the sol-gel process. Detailed inspection of the (1)H and (13)C VT NMR spectra of mixtures with different Li/Ti atomic ratios unequivocally shows the formation of [LiTi3(OEt)13] in a solution at low temperature. The methylene signals of free lithium ethoxide and Li[Ti3(OEt)13] coalesce at 20 °C when the atomic ratio is 5 : 5; however, the same coalescence is only observed above 60 °C when the atomic ratio is 4 : 5. We suggest that the highest chemical equivalence observed by (1)H NMR spectroscopy achieved through chemical exchange of ethoxide groups involves the highest microscopic structural homogeneity of the sol precursor and will lead to the best gel after hydrolysis. Variable temperature (1)H NMR spectra at 400 MHz of variable molar ratios of LiOEt/Ti(OPr(i))4 are discussed to understand the structural features of the sol precursor. While the precursor with the atomic ratio 5Li : 5Ti shows no signal of free LiOEt at 20 °C, both 4Li : 5Ti and 7Li : 5Ti show free LiOEt at 20 °C in their (1)H NMR spectra, indicating that the molar ratio 5Li : 5Ti gives the maximum rate of chemical exchange. DFT calculations have been performed to support the structure of the anion [Ti3(OEt)13](-) at room temperature.

Nanoporous piezo- and ferroelectric thin films.

Nanoporous barium titanate and lead titanate thin films (∼100 nm calculated from ellipsometric data) are prepared starting from sol-gel solutions modified with a commercially available block-copolymer and evaporation-induced self-assembly methodology. The tuning of the thermal treatment followed by in situ ellipsometry allows the decomposition of the organic components and of the structuring agent leading to the formation of porous tetragonal crystalline perovskite structures as observed by XRD, HRTEM, SEM, and ellipsoporosimetry. Both nanoporous barium titanate and lead titanate thin films present local piezoelectric and ferroelectric behavior measured by piezoresponse force microscopy (PFM), being promising platforms for the preparation of the generation of new multifunctional systems.