Comparing the Performance of Nb2O5 Composites with Reduced Graphene Oxide and Amorphous Carbon in Li‐ and Na‐Ion Electrochemical Storage Devices

Two‐dimensional (2D) reduced graphene oxide (rGO) is often combined with metal oxides for energy‐storage applications, owing to its unique properties. Here, we compare the electrochemical performance of Nb2O5‐rGO and amorphous carbon‐coated‐Nb2O5 composites, synthesized in similar conditions. The composite made of Nb2O5 and amorphous carbon (using 1,3,5‐triphenylbenzene as carbon source) outperforms the Nb2O5‐rGO counterpart as a high rate anode electrode material in Li‐ion and Na‐ion half‐cells and hybrid supercapacitors, delivering specific capacities of 134 mAh g−1 at 25 C against 98 mAh g−1 for the rGO‐based composite (in Li electrolyte) and 125 mAh g−1 at 20 C against 98 mAh g−1 (in Na electrolyte). The organic molecules, which are the precursor of the amorphous carbon, control the size and coat the metal oxide particles more efficiently, leading to more extensive carbon‐oxide contacts, which benefits the energy‐storage performance.Peer Reviewe

Influence of the Cobalt Phase on the Highly Efficient Growth of MWNTs

In this work, the influence of the cobalt phase on the growth of carbon nanotubes by the catalytic chemical vapour deposition of CH4 with catalysts containing Co, Mo and Mg is investigated. To this end, the catalytic behaviour of physically mixed CoO/MgO+MgMoO4 and CoMoO4+MgMoO4 is studied. The results obtained show that CoMoO4+MgMoO4 allows for the attainment of the highest CNT yield (2407 wt % against 1296 wt %). Its higher activity is ascribed to the greater formation of active sites that, in light of current assessments, are constituted by metallic cobalt adjacent to Mo2C, and the huge exfoliation of the catalyst, which contributes towards enhancing their exposure

Exploiting the Condensation Reactions of Acetophenone to Engineer Carbon-Encapsulated Nb2O5 Nanocrystals for High-Performance Li and Na Energy Storage Systems

Efficient synthetic methods to produce high‐performance electrode‐active materials are crucial for developing energy storage devices for large‐scale applications, such as hybrid supercapacitors (HSCs). Here, an effective approach to obtain controllable carbon‐encapsulated T‐Nb2O5 nanocrystals (NCs) is presented, based on the solvothermal treatment of NbCl5 in acetophenone. Two separate condensation reactions of acetophenone generate an intimate and homogeneous mixture of Nb2O5 particles and 1,3,5‐triphenylbenzene (TPB), which acts as a unique carbon precursor. The electrochemical performance of the resulting composites as anode electrode materials can be tuned by varying the Nb2O5/TPB ratio. Remarkable performances are achieved for Li‐ion and Na‐ion energy storage systems at high charge–discharge rates (specific capacities of ≈90 mAh g−1 at 100 C rate for lithium and ≈125 mAh g−1 at 20 C for sodium). High energy and power densities are also achieved with Li‐ and Na‐ion HSC devices constructed by using the Nb2O5/C composites as anode and activated carbon (YPF‐50) as cathode, demonstrating the excellent electrochemical properties of the materials synthesized with this approach.Peer Reviewe

Bacterial-cellulose-derived carbonaceous electrode materials for water desalination via capacitive method: The crucial role of defect sites

Electrosorptive desalination is a very simple and appealing approach to satisfy the increasing demand for drinking water. The large-scale application of this technology calls for the development of easy-to-produce, cheap and highly performing electrode materials and for the identification and tailoring of their most influential properties, as well. Here, biosynthesised bacterial cellulose is used as a carbon precursor for the production of three-dimensional nanostructures endowed with hierarchically porous architecture and different density and type of intrinsic and hetero-atom induced lattice defects. The produced materials exhibit unprecedented desalination capacities for carbon-based electrodes. At an initial concentration of 585 mg L−1 (10 mmol L−1), they are able to remove from 55 to 79 mg g−1 of salt; as the initial concentration rises to 11.7 g L−1 (200 mmol L−1), their salt adsorption capacity reaches values ranging between 1.03 and 1.35 g g−1. The results of the thorough material characterisation by complementary techniques evidence that the relative amount of oxygenated surface functional species enhancing the electrode wettability play a crucial role at lower NaCl concentrations, whereas the availability of active non-sp2 defect sites for adsorption is mainly influential at higher salt concentrations.L.U., M.A.C. and A.E. gratefully thank GIU18/216 - UPV/EHU Research Group for the financial support to their work

Comparative life cycle assessment of Fe2O3-based fibers as anode materials for sodium-ion batteries

AbstractSodium-ion batteries (SIBs) potentially represent a more sustainable, less expensive and environmentally friendly alternative to lithium-ion batteries. The development of new low-cost, non-toxic, highly performing electrode materials is the key point for the SIB technology advances. This study develops a basic life cycle assessment (LCA) model for the evaluation of the production by electrospinning of iron (III) oxide-based fibers to be used as anode materials in SIBs. Indeed, it has been recently demonstrated that electrospun silicon-doped iron (III) oxide (Fe2O3) fibers exhibit outstanding electrochemical properties and gravimetric capacities never achieved before for pure Fe2O3-based anodes. The LCA methodology is utilized in order to analyze the environmental burdens (from raw material extraction to manufacturing process) of these electrode materials. The simplified comparative LCA studies, conducted to assess the environmental impacts associated with the electrospun Fe2O3 and Fe2O3:Si fibers at the same cell performance, demonstrate that the Si-doped anode material, which exhibits better electrochemical performance with respect to the undoped one, has also lower impact for each category of damage, namely human health, ecosystem quality and resources

High-Entropy Spinel Oxides Produced via Sol-Gel and Electrospinning and Their Evaluation as Anodes in Li-Ion Batteries

In the last few years, high-entropy oxides (HEOs), a new class of single-phase solid solution materials, have attracted growing interest in both academic research and industry for their great potential in a broad range of applications. This work investigates the possibility of producing pure single-phase HEOs with spinel structure (HESOs) under milder conditions (shorter heat treatments at lower temperatures) than standard solid-state techniques, thus reducing the environmental impact. For this purpose, a large set of HESOs was prepared via sol-gel and electrospinning (by using two different polymers). Ten different equimolar combinations of five metals were considered, and the influence of the synthesis method and conditions on the microstructure, morphology and crystalline phase purity of the produced HESOs was investigated by a combination of characterization techniques. On the other hand, the presence of specific metals, such as copper, lead to the formation of minority secondary phase(s). Finally, two representative pure single-phase HESOs were preliminarily evaluated as active anode materials in lithium-ion batteries and possible strategies to enhance their rate capability and cyclability were proposed and successfully implemented. The approaches introduced here can be extensively applied for the optimization of HEO properties targeting different applications.Italian Ministry of University and Research (MUR)Peer Reviewe

Niobium pentoxide nanomaterials with distorted structures as efficient acid catalysts

Niobium pentoxides are promising acid catalysts for the conversion of biomass into fuels and chemicals. Developing new synthesis routes is essential for designing niobium pentoxide catalysts with improved activity for specific practical processes. Here we show a synthesis approach in acetophenone, which produces nanostructured niobium pentoxides with varying structure and acidity that act as efficient acid catalysts. The oxides have orthorhombic structures with different extents of distortions and coordinatively unsaturated metal atoms. A strong dependence is observed between the type and strength of the acid sites and specific structural motifs. Ultrasmall niobium pentoxide nanoparticles, which have strong Brønsted acidity, as well as Lewis acidity, give product yields of 96% (3 h, 140 °C, 100% conversion), 85% (3 h, 140 °C, 86% conversion), and 100% (3 h, 110 °C, 100% conversion) in the reactions of furfuryl alcohol, 5-(hydroxymethyl)furfural, and α-angelica lactone with ethanol, respectively.Peer Reviewe

On the CVD Growth of C Nanotubes Over Fe-Loaded Montmorillonite Catalysts

The synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) of isobutane (i‐C4H10) over sodium‐exchanged K10‐montmorillonite based iron‐ catalysts is investigated. By studying the influence of iron‐addition (5–25wt%) on the catalyst performances, at 700 °C, an empirical relationship is derived relating the mass of CNTs synthesized with the exposed surface of loaded iron, as resulting from simultaneous change of number, size and dispersion of Fe‐nanoparticles available for the growth

Electro-spun graphene-enriched carbon fibres with high nitrogen-contents for electrochemical water desalination

Electro-spun carbon fibres doped with very high nitrogen concentrations (19–21 wt%) are obtained operating carbonisation at low temperature (500 °C). The as-synthesised fibres are evaluated as electrode materials for the electrochemical desalination of water. The effect of the enrichment of the nitrogen doped carbon fibres with thermally reduced graphene oxide is also investigated. The fibrous electrodes are able to remove amazing amounts of NaCl (17.0–27.6 mg/g) from a salty solution with an initial concentration of 585 mg/L. The nitrogen doping, which dramatically improves the wettability, plays a crucial role in determining the outstanding electro-sorption capacities of the fibres. It allows fully profiting of the more favourable pore size distribution in the graphene-enriched fibres, endowed with higher conductivity and capacitance, for the obtainment of unprecedented electro-sorption capacities via an extremely simple synthesis process, with no need of activation treatments

Synergistic Effects of Active Sites' Nature and Hydrophilicity on Oxygen Reduction Reaction Activity of Pt-Free Catalysts

This work highlights the importance of the hydrophilicity of a catalyst’s active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu