Reduced Graphene Oxide Embedded with ZnS Nanoparticles as Catalytic Cathodic Material for Li-S Batteries.

Lithium-sulfur technology is a strong candidate for the future generation of batteries due to its high specific capacity (1675 mAh g-1), low cost, and environmental impact. In this work, we propose a facile and solvent-free microwave synthesis for a composite material based on doped (sulfur and nitrogen) reduced graphene oxide embedded with zinc sulfide nanoparticles (SN-rGO/ZnS) to improve the battery performance. The chemical-physical characterization (XRD, XPS, FESEM, TGA) confirmed the effectiveness of the microwave approach in synthesizing the composite materials and their ability to be loaded with sulfur. The materials were then thoroughly characterized from an electrochemical point of view (cyclic voltammetry, galvanostatic cycling, Tafel plot, electrochemical impedance spectroscopy, and Li2S deposition test); the SN-rGO/ZnS/S8 cathode showed a strong affinity towards polysulfides, thus reducing their loss by diffusion and improving redox kinetics, allowing for faster LiPSs conversion. In terms of performance, the composite-based cathode increased the specific capacity at high rate (1 C) from 517 to 648 mAh g-1. At the same time, more stable behavior was observed at 0.5 C with capacity retention at the 750th cycle, where it was raised from 32.5% to 48.2%, thus confirming the beneficial effect of the heteroatomic doping process and the presence of zinc sulfide nanoparticles.

Micro-Mesoporous Carbons from Cyclodextrin Nanosponges Enabling High-Capacity Silicon Anodes and Sulfur Cathodes for Lithiated Si-S Batteries.

Manufactured globally on industrial scale, cyclodextrins (CD) are cyclic oligosaccharides produced by enzymatic conversion of starch. Their typical structure of truncated cone can host a wide variety of guest molecules to create inclusion complexes; indeed, we daily use CD as unseen components of food, cosmetics, textiles and pharmaceutical excipients. The synthesis of active material composites from CD resources can enable or enlarge the effective utilization of these products in the battery industry with some economical as well as environmental benefits. New and simple strategies are here presented for the synthesis of nanostructured silicon and sulfur composite materials with carbonized hyper cross-linked CD (nanosponges) that show satisfactory performance as high-capacity electrodes. For the sulfur cathode, the mesoporous carbon host limits polysulfide dissolution and shuttle effects and guarantees stable cycling performance. The embedding of silicon nanoparticles into the carbonized nanosponge allows to achieve high capacity and excellent cycling performance. Moreover, due to the high surface area of the silicon composite, the characteristics at the electrode/electrolyte interface dominate the overall electrochemical reversibility, opening a detailed analysis on the behavior of the material in different electrolytes. We show that the use of commercial LP30 electrolyte causes a larger capacity fade, and this is associated with different solid electrolyte interface layer formation and it is also demonstrated that fluoroethylene carbonate addition can significantly increase the capacity retention and the overall performance of our nanostructured Si/C composite in both ether-based and LP30 electrolytes. As a result, an integration of the Si/C and S/C composites is proposed to achieve a complete lithiated Si-S cell.

Nanosponge-Based Composite Gel Polymer Electrolyte for Safer Li-O2 Batteries.

Li-O2 batteries represent a promising rechargeable battery candidate to answer the energy challenges our world is facing, thanks to their ultrahigh theoretical energy density. However, the poor cycling stability of the Li-O2 system and, overall, important safety issues due to the formation of Li dendrites, combined with the use of organic liquid electrolytes and O2 cross-over, inhibit their practical applications. As a solution to these various issues, we propose a composite gel polymer electrolyte consisting of a highly cross-linked polymer matrix, containing a dextrin-based nanosponge and activated with a liquid electrolyte. The polymer matrix, easily obtained by thermally activated one pot free radical polymerization in bulk, allows to limit dendrite nucleation and growth thanks to its cross-linked structure. At the same time, the nanosponge limits the O2 cross-over and avoids the formation of crystalline domains in the polymer matrix, which, combined with the liquid electrolyte, allows a good ionic conductivity at room temperature. Such a composite gel polymer electrolyte, tested in a cell containing Li metal as anode and a simple commercial gas diffusion layer, without any catalyst, as cathode demonstrates a full capacity of 5.05 mAh cm-2 as well as improved reversibility upon cycling, compared to a cell containing liquid electrolyte.

Role of the solvent in the activation of Li2S as cathode material: a DFT study.

Lithium-sulfur batteries are considered one of the possible next-generation energy-storage solutions, but to be commercially available many drawbacks have yet to be solved. One solution with great potentiality is the use of lithium sulfide as cathode material since it can be coupled to Li-free anodes, such as graphite, Si or Sn. Nevertheless, Li2S, like sulfur, is electronically and ionically insulating, with a high activation potential for its initial oxidation step. To overcome this issue, different strategies have been explored, one of them being the use of catalytic surfaces. In the present article, we study using first principles calculations the effect of the dielectric constant of the solvent on the activation energy of the cleavage reaction of Li2S on different catalytic surfaces. To the best of our knowledge, this is the first time that such a study is undertaken. We find that the effect of the solvent should be twofold: on one side, it should decrease the interaction between the Li2S molecule and the surface. On the other side, since the species arising in the dissociation reaction are charged, the solvent should decrease the activation barrier for the dissociation of the Li2S molecule, when compared with the reaction in vacuum. These theoretical findings are discussed in connection with experimental results from the literature, where the behaviour of the Li-S cathode is studied in different solvents.

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.).

Tragacanth Gum as Green Binder for Sustainable Water-Processable Electrochemical Capacitor.

Enabling green fabrication processes for energy storage devices is becoming a key aspect in order to achieve a sustainable fabrication cycle. Here, the focus was on the exploitation of the tragacanth gum, an exudated gum like arabic and karaya gums, as green binder for the preparation of carbon-based materials for electrochemical capacitors. The electrochemical performance of tragacanth (TRGC)-based electrodes was thoroughly investigated and compared with another water-soluble binder largely used in this field, sodium-carboxymethyl cellulose (CMC). Apart from the higher sustainability both in production and processing, TRGC exhibited a lower impact on the obstruction of pores in the final active material film with respect to CMC, allowing for more available surface area. This directly impacted the electrochemical performance, resulting in a higher specific capacitance and better rate capability. Moreover, the TRGC-based supercapacitor showed a superior thermal stability compared with CMC, with a capacity retention of about 80 % after 10000 cycles at 70 °C.