Electrochem, Volume 1, Issue 2 (June 2020) – 8 articles

Voltage vs. time curves of double layer capacitances (DLCs) by current-controlled charge and discharge steps have been recognized to be composed of triangular waves. They are deviated slightly from triangles from the viewpoint of the time dependence or the constant phase element of the DLC. In order to evaluate the deviation, we measured DLCs of a platinum (Pt) electrode in KCl solution by current-control. Each time-voltage curve was convex rather a line, and was followed by the power law. Even if the time dependence was subtracted from each curve, the enhancement of the DLC was noticeable with an increase in the time well as the voltage. It can be attributed to the electric field effect, in which dipoles of solvents are oriented on an electrode so strongly that the DLC may be increased. The field dependence can be justified with the kinetic theory of interacting dipoles of solvents on an electrode through the observed linearity of the logarithmic DLC with the net voltage. This concept was applied to a commercially available super-capacitor to demonstrate a significant contribution of the field effect. Full article

Sulphur, boron and phosphorous containing electrolyte additives were evaluated in cells containing pristine electrodes from a commercial EV lithium ion cell against a standard baseline electrolyte. Following formation and a full cell ageing step, cycling performance and impedance spectroscopy were used to elucidate the most effective additives. The additive tris trimethyl silyl phosphite (TTSPi) showed the most promise; with improved cell capacities and reduced impedances observed after formation. X-ray photoelectron spectroscopy (XPS) measurements on anode elemental surface profiles were correlated with the electrochemical performance. It was observed that increased lithium fluoride content on the surface of the anodes typically produced cells with lower impedance. Sulphur containing additives also showed improved cell behaviours; and the decomposition and chemical reactions of these compounds at the anode surface is discussed in detail. The main influence of TTSPi was to reduce the amount of oxygen (C=O) and sulphur in the electrolyte interphase (SEI) layer; to be replaced with hydrocarbons. Full article

The corrosion of mild steel in aqueous perchloric acid solution was studied in the presence and absence of four different pyridine derivatives. Electrochemical measurements point out that these molecules inhibit the corrosion of mild steel by acting as mixed inhibitors. The adsorbed molecules act as a barrier that prevents the oxidation of the metal and the hydrogen evolution reaction at the mild steel surface. Molecular insights vis-à-vis the corrosion process were acquired by the use of Density Functional Theory (DFT), Molecular Dynamics, and Monte Carlo calculations. Monte Carlo and Molecular Dynamic simulation were used to understand at the molecular level the adsorption ability of the studied molecules onto Fe(110) surface. The experimental results and theoretical calculations provided important support for the understanding of the corrosion inhibition mechanism expressed by the pyridine molecules. Full article

In this paper, we investigate the effects of operational conditions on structural, electronic and electrochemical properties on molybdenum suboxides (MoO_3-δ) thin films. The films are prepared using pulsed-laser deposition by varying the deposition temperature (T_s), laser fluence (Φ), the partial oxygen pressure (P_O2) and annealing temperature (T_a). We find that three classes of samples are obtained with different degrees of stoichiometric deviation without post-treatment: (i) amorphous MoO_3-δ (δ < 0.05) (ii) nearly-stoichiometric samples (δ ≈ 0) and (iii) suboxides MoO_3-δ (δ > 0.05). The suboxide films 0.05 ≤ δ ≤ 0.25 deposited on Au/Ti/SiO₂/flexible-Si substrates with appropriate processing conditions show high electrochemical performance as an anode layer for lithium planar microbatteries. In the realm of simple synthesis, the MoO_3-δ film deposited at 450 °C under oxygen pressure of 13 Pa is a mixture of α-MoO₃ and Mo₈O₂₃ phases (15:85). The electrochemical test of the 0.15MoO₃-0.85Mo₈O₂₃ film shows a specific capacity of 484 µAh cm⁻² µm⁻¹ after 100 cycles of charge-discharge at a constant current of 0.5 A cm⁻² in the potential range 3.0-0.05 V. Full article

Current collectors (CCs) are an important and indispensable constituent of lithium-ion batteries (LIBs) and other batteries. CCs serve a vital bridge function in supporting active materials such as cathode and anode materials, binders, and conductive additives, as well as electrochemically connecting the overall structure of anodes and cathodes with an external circuit. Recently, various factors of CCs such as the thickness, hardness, compositions, coating layers, and structures have been modified to improve aspects of battery performance such as the charge/discharge cyclability, energy density, and the rate performance of a cell. In this paper, the details of interesting and useful attempts of preparing CCs for high battery performance in lithium-ion and post-lithium-ion batteries are reviewed. The advantages and disadvantages of these attempts are discussed. Full article

On the basis of a survey on the relevant literature it can be stated that some views and approaches concerning the charged state of adsorbed species and the charge transfer processes occurring with them are far from being unambiguous even in some respect they contradict fundamental physical and physicochemical principles. The meaning of the electrosorption valency, the misleading formulation of the Gibbs adsorption equation, and the interpretation of redox processes occurring with adsorbed species, is discussed in detail. It has been concluded that although the electrosorption valency of an adsorbed species as usually defined is an extra-thermodynamic and self-contradictory concept, experimental determined formal partial charge numbers can be a useful tool for scientists investigating adsorption phenomena, since the observed deviation between its value and the charge number of the same species in the solution phase unequivocally indicates a non-simple mechanism of the adsorption process, which should be taken into account in theoretical interpretation of the experimental data. It has been emphasized that the evaluation of voltammetric curves obtained in the presence of adsorbed redox partners requires a cautious analysis of the accompanying chemical transformations. In the framework of a critical analysis it is demonstrated that probably one of the most important sources of the misinterpretations and misunderstandings is the inadequate approach to the concept of electrode charge. The possibility of a general and straightforward presentation of the Gibbs adsorption equation has also been discussed. Full article

The purpose of this study was to explain the mechanism of formation and to examine the composition of the anodic film formed on the surface of titanium in an anhydrous neutral methanol solution of electrolytes. In an environment deprived of water molecules, the growth of a 3D-phase titanium oxide layer is not possible. Electrochemical investigations demonstrated that the Ti surface in CH₃OH-LiClO₄ solutions experienced a pseudo-passivation with the formation of a methoxy layer, which resulted from the reaction of the metal surface with alcohol molecules. The presence of this methoxy surface film was confirmed through XPS and in situ FTIR measurements. The layer blocked the Ti anodic dissolution at the potential range corresponding to the stability of methanol and methoxy ions (i.e., <0.55 V). At potentials over 0.55 V, the methoxy layer was oxidised, which caused the “depassivation” of the metal surface and the etching of titanium. The addition of water changed the properties of Ti in CH₃OH-LiClO₄ solutions, but only with a water content above 0.2 mole fraction. Below this concentration of water, titanium behaved like it would in an anhydrous solution of methanol. In the range of water concentration of 0.2 to 0.7 mole fraction, the structure of the solution is strengthened because both components of the solvent formed separate percolating networks. The strengthening of the solution structure resulted in a strengthening of the surface layer of Ti(OH)_m(OCH₃)_n. Such a layer had strong barrier properties similar to the properties of an organic polymer film. The formation and growth of a stable layer of TiO₂ were possible only in a solvent when the water concentration was higher than ≈0.7 mole fraction. Full article

Developing sustainable and renewable energy sources is critical as higher and higher global energy and environmental challenges arise. Hydrogen has the highest mass/energy density of any fuel and is considered one of the best sources of clean energy. Water splitting is regarded as one of the most promising solutions for hydrogen production on a large scale. Highly efficient, durable, and cost-effective catalysts for hydrogen evolution reaction (HER) are critical in the realization of this goal. Among the many materials proposed, graphene-based materials offer some unique properties for HER catalysis. In this review, we present recent progress on development of graphene-based electrocatalysts toward HER throughout the past few years. Full article