Probing the interaction mechanism of heterostructured VOxNy nanoparticles supported in nitrogen-doped reduced graphene oxide aerogel as an efficient polysulfide electrocatalyst for stable sulfur cathodes

Reversible redox of sulfur to lithium sulfide through a series of lithium polysulfides (LiPS) still pose a key challenge to appreciate high-performance sulfur cathodes mainly because of shuttling phenomenon and sluggish kinetics. Herein, a simple novel synthetic approach has been presented to realize porous vanadium nitride oxide (VOxNy) nanoparticles spatially decorated within nitrogen doped reduced graphene aerogel (VONNG) via concurrent in-situ nitridation and carbonization processes. Nitrogen-doped reduced graphene aerogel enhances the physical retention and polar interaction of LiPS and contributes toward the overall conductivity of the matrix. Whereas, vanadium nitride oxide has exhibited a redox potential window intermediate to its oxides’ counterparts around which LiPS can form polythionate complexes to enhance the kinetics and LiPS retention by exploiting the V–N and V–O interfaces at cathode. The interaction mechanism has been probed through in-operando Raman spectroscopy, XPS and electroanalytical methods. The assembled cells from VONNG/S cathodes exhibit the initial discharge capacity of 1400 mAh g−1 at 0.05 C, 1250 mAh g−1 at 0.1 C and maintained reversible capacity about 700 mA h g−1 at 0.2 C after 200 cycles. The loss in capacity is less than 0.05% per cycle for 850 cycles with Coulombic efficiency close to 99% even at 5C

An Overview on Anodes for Magnesium Batteries: Challenges towards a Promising Storage Solution for Renewables

Magnesium-based batteries represent one of the successfully emerging electrochemical energy storage chemistries, mainly due to the high theoretical volumetric capacity of metallic magnesium (i.e., 3833 mAh cm−3 vs. 2046 mAh cm−3 for lithium), its low reduction potential (−2.37 V vs. SHE), abundance in the Earth’s crust (104 times higher than that of lithium) and dendrite-free behaviour when used as an anode during cycling. However, Mg deposition and dissolution processes in polar organic electrolytes lead to the formation of a passivation film bearing an insulating effect towards Mg2+ ions. Several strategies to overcome this drawback have been recently proposed, keeping as a main goal that of reducing the formation of such passivation layers and improving the magnesium-related kinetics. This manuscript offers a literature analysis on this topic, starting with a rapid overview on magnesium batteries as a feasible strategy for storing electricity coming from renewables, and then addressing the most relevant outcomes in the field of anodic materials (i.e., metallic magnesium, bismuth-, titanium- and tin-based electrodes, biphasic alloys, nanostructured metal oxides, boron clusters, graphene-based electrodes, etc.)

Gelatine based gel polymer electrolyte towards more sustainable Lithium-Oxygen batteries

The lithium-oxygen battery has attracted wide interest thanks to its very high theoretical energy density, and as such it is considered by many as a valid battery of the future candidate. However, the challenges in its practical application are many, such as liquid electrolyte evaporation in semi-open systems, as well as solvents instability in a highly oxidizing environment. In this work, we propose to use gelatin, from cold water fish skin, a waste from the fishing industry, to prepare an efficient gel electrolyte for future Li-O2 battery applications. After a single step methacrylation in water, methacrylated gelatine is directly cross-linked in presence of liquid electrolyte through UV- initiated radical polymerization. The obtained gel polymer electrolytes present good thermal and mechanical properties, good electrochemical stability against Li metal and ionic conductivities as high as 2.51 mS cm−1 at room temperature. the Li-O2 cells assembled with this bio-renewable gel polymer electrolytes were able to perform more than 100 cycles at 0.1 mA cm−2, under constant O2 flow, at room temperature and at a fixed capacity of 0.2 mAh cm−2. Cathodes post- mortem analysis confirmed that the cross-linked gelatin matrix was able to slow down solvent degradation and therefore enhance the cell reversibility

Synthesis and characterization of LNMO cathode materials for lithium-ion batteries

Abstract Synthesis of LiNi0.5Mn1.5O4 (LNMO), a promising cathode material for next generation lithium-ion batteries, was performed via Liquid Phase Self-propagating High-temperature Synthesis (LPSHS) and Aerosol Spray Pyrolysis (ASP) techniques. In the case of the LPSHS technique, the effect of the "fuel" quantity of the precursor solution on the structure, morphology and electrochemical performance of the materials was studied, while in the case of the ASP technique the effect of eight different calcination profiles on the structure, morphology, crystalline phase and electrochemical performance of the material. Structural characterization was performed through XRD, SEM, TEM, BET and Raman spectroscopy, while the electrochemical activity was evaluated via charge/discharge galvanostatic characterization. The results showed that the optimal LPSHS material was obtained for a molar ratio of metal ions/fuel = 3:1 exhibiting stable specific capacity over the cycles even by increasing the C-rate. Τhe optimal ASP material was identified in the case of calcination at 850°C. Both materials had the disordered Fd-3m structure of the LNMO spine

An exploratory study of MoS2 as anode material for potassium batteries

Potassium-based batteries represent one of the emerging classes of post-lithium electrochemical energy storage systems in the international scene, due to both the abundance of raw materials and achievable cell potentials not far from those of lithium batteries. In this context, it is important to define electrodes and electrolytes that give reproducible performance and that can be used by different research groups as an internal standard when developing new materials. We propose molybdenum disulfide (MoS2) as a valid anode choice, being a commercial and easily processable material, the 2D layered structure of which is promising for large potassium ions reversible storage. It has been proven to work for hundreds of cycles, keeping a constant specific capacity around 100 mAh g−1 while also preserving its electrochemical interphase and morphology

Li+ Insertion in Nanostructured TiO2 for Energy Storage

Nanostructured materials possess unique physical-chemical characteristics and have attracted much attention, among others, in the field of energy conversion and storage devices, for the possibility to exploit both their bulk and surface properties, enabling enhanced electron and ion transport, fast diffusion of electrolytes, and consequently high efficiency in the electrochemical processes. In particular, titanium dioxide received great attention, both in the form of amorphous or crystalline material for these applications, due to the large variety of nanostructures in which it can be obtained. In this paper, a comparison of the performance of titanium dioxide prepared through the oxidation of Ti foils in hydrogen peroxide is reported. In particular, two thermal treatments have been compared. One, at 150 °C in Ar, which serves to remove the residual hydrogen peroxide, and the second, at 450 °C in air. The material, after the treatment at 150 °C, results to be not stoichiometric and amorphous, while the treatment at 450 °C provide TiO2 in the anatase form. It turns out that not-stoichiometric TiO2 results to be a highly stable material, being a promising candidate for applications as high power Li-ion batteries, while the anatase TiO2 shows lower cyclability, but it is still promising for energy-storage devices

Fast Switching Electrochromic Devices Containing Optimized BEMA/PEGMA Gel Polymer Electrolytes

An optimized thermoset gel polymer electrolyte based on Bisphenol A ethoxylate dimethacrylate and Poly(ethylene glycol) methyl ether methacrylate (BEMA/PEGMA) was prepared by facile photo-induced free radical polymerisation technique and tested for the first time in electrochromic devices (ECD) combining WO3 sputtered on ITO as cathodes and V2O5 electrodeposited on ITO as anodes. The behaviour of the prepared ECD was investigated electrochemically and electro-optically. The ECD transmission spectrum was monitored in the visible and near-infrared region by varying applied potential. A switching time of ca. 2 s for Li+ insertion (coloring) and of ca. 1 s for Li+ de-insertion (bleaching) were found. UV-VIS spectroelectrochemical measurements evidenced a considerable contrast between bleached and colored state along with a good stability over repeated cycles. The reported electrochromic devices showed a considerable enhancement of switching time with respect to the previously reported polymeric ECD indicating that they are good candidates for the implementation of intelligent windows and smart displays

Platinum-free photoelectrochromic devices working with copper-based electrolytes for ultrastable smart windows

Photoelectrochromic systems are devices designed for large-scale manufacturing of smart windows, capable of changing their transmittance according to external environmental conditions. This communication proposes the replacement of the two most critical photoelectrochemical device components studied so far, namely the counter electrode and the redox mediator. Regarding the first, graphene nanoplatelets are used to replace platinum, maintaining both its optical and electrocatalytic properties, and at the same time reducing the device cost. Secondly, a copper-based redox pair was chosen to solve the corrosion problems typically encountered with the iodine-based mediator. The combination of the above components led to devices with high performance (coloration speeds in the order of seconds, with a maximum contrast ratio of 10.4 : 1), as well as the achievement of a long-term stability record (over 400 days) for these photoelectrochromic systems