Electrochem, Volume 2, Issue 1 (March 2021) – 12 articles

Among the many biological entities employed in the development of biosensors, enzymes have attracted the most attention. Nanotechnology has been fostering excellent prospects in the development of enzymatic biosensors, since enzyme immobilization onto conductive nanostructures can improve characteristics that are crucial in biosensor transduction, such as surface-to-volume ratio, signal response, selectivity, sensitivity, conductivity, and biocatalytic activity, among others. These and other advantages of nanomaterial-based enzymatic biosensors are discussed in this work via the compilation of several reports on their applications in different industrial segments. To provide detailed insights into the state of the art of this technology, all the relevant concepts around the topic are discussed, including the properties of enzymes, the mechanisms involved in their immobilization, and the application of different enzyme-derived biosensors and nanomaterials. Finally, there is a discussion around the pressing challenges in this technology, which will be useful for guiding the development of future research in the area. Full article

This paper proposes a novel He-based cooling system for the Li-ion batteries (LIBs) used in electric vehicles (EVs) and hybrid electric vehicles (HEVs). The proposed system offers a novel alternative battery thermal management system with promising properties in terms of safety, simplicity, and efficiency. A 3D multilayer coupled electrochemical-thermal model is used to simulate the thermal behavior of the 20 Ah LiFePO₄ (LFP) cells. Based on the results, He gas, compared to air, effectively diminishes the maximum temperature rise and temperature gradient on the cell surface and offers a viable option for the thermal management of Li-ion batteries. For instance, in comparison with air, He gas offers 1.18 and 2.29 °C better cooling at flow rates of 2.5 and 7.5 L/min, respectively. The cooling design is optimized in terms of the battery’s temperature uniformity and the battery’s maximum temperature. In this regard, the effects of various parameters such as inlet diameter, flow direction, and inlet flow rate are investigated. The inlet flow rate has a more evident influence on the cooling efficiency than inlet/outlet diameter and flow direction. The possibility of using helium as a cooling fluid is shown to open new doors in the subject matter of an effective battery thermal management system. Full article

Wearable self-powered sensors represent a theme of interest in the literature due to the progress in the Internet of Things and implantable devices. The integration of different materials to harvest energy from body movement or the environment to power up sensors or act as an active component of the detection of analytes is a frontier to be explored. This review describes the most relevant studies of the integration of nanogenerators in wearables based on the interaction of piezoelectric and triboelectric devices into more efficient and low-cost harvesting systems to power up batteries or to use the generated power to identify multiple analytes in self-powered sensors and biosensors. Full article

This work presents a contribution to the study of a new Ni-rich spinel cathode material, LiNiMnO₄, for Li-ion batteries operating in the 5-V region. The LiNiMnO₄ compound was synthesized by a sol-gel method assisted by ethylene diamine tetra-acetic acid (EDTA) as a chelator. Structural analyses carried out by Rietveld refinements and Raman spectroscopy, selected area electron diffraction (SAED) and X-ray photoelectron (XPS) spectroscopy reveal that the product is a composite (LNM@NMO), including non-stoichiometric LiNiMnO_4-δ spinel and a secondary Ni₆MnO₈ cubic phase. Cyclic voltammetry and galvanostatic charge-discharge profiles show similar features to those of LiNi_0.5Mn_1.5O₄ bare. A comparison of the electrochemical performances of 4-V spinel LiMn₂O₄ and 5-V spinel LiNi_0.5Mn_1.5O₄ with those of LNM@NMO composite demonstrates the long-term cycling stability of this new Ni-rich spinel cathode. Due to the presence of the secondary phase, the LNM@NMO electrode exhibits an initial specific capacity as low as 57 mAh g⁻¹ but shows an excellent electrochemical stability at 1C rate for 1000 cycles with a capacity decay of 2.7 × 10⁻³ mAh g⁻¹ per cycle. Full article

Ruthenium oxide (RuOx) thin films were spin coated by thermal decomposition of alcoholic solutions of RuCl₃ on titanium foils and subsequently annealed at 400 °C. The effect of spin coating parameters, such as spinning speed, volume, and molar concentration of the precursor as well as the number of deposits, on the morphology and electrochemical performance of the electrodes was investigated. The films were characterized by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV) with and without chloride, and linear sweep voltammetry (LSV). The prepared materials were also compared to drop cast films and spin-coated films obtained by adopting low-temperature intermediate treatments. The results indicate that even dispersion of the oxide layer was always achieved. By tuning the spin coating parameters, it was possible to obtain different electrochemical responses. The most influential parameter is the number of deposits, while the concentration of the precursor salt and the rotation speed were less relevant, under the adopted conditions. Full article

A double layer capacitance (DLC) has mainly been brought about in the Helmholtz layer rather than in the diffuse layer, as was demonstrated with the invariance of DLC to salt concentration, c, less than 0.5 M (M = mol dm⁻³). The DLC measured here increased with concentrations of KCl and HCl solutions as high as 1 M at a platinum electrode by the ac impedance method. It was represented as a sum of the Helmholtz capacitance and the ionic one which had 0.7 power of the concentrations. The simple addition implies that the Helmholtz contribution and the ionic one should be represented by a parallel combination rather than a series one such as in the Stern model. The disagreement of the experimental values of the DLC with the Gouy–Chapman theory at high concentrations has been conventionally attributed to the effects of packing of ions over their sizes. In this paper, a model of avoiding the packing was introduced, in which ions were distributed in the direction normal to the electrode in the balance of electric motive force and the thermal energy, keeping the uniform distribution on a plane projected to the electrode. The energy balance was taken by using the grand canonical ensemble in statistical mechanics. The ionic contribution had a linear relation with the applied voltage rather than exponential dependence. When a series combination was applied to the Helmholtz capacitance and the ionic one under the condition of difference between the locally anionic DLC and the cationic one, we obtained approximately a parallel combination of the two capacitances because either the anionic or the cationic DLC works predominantly. Full article

Nowadays, the self-accelerating increase in global temperatures strengthens the idea that the cutting of CO₂ emissions will not be enough to avoid climate change, thus CO₂ from the atmosphere must be removed. This gas can be easily trapped by converting it to bicarbonate using hydroxide solutions. However, bicarbonate must be converted into a more valuable product to make this technology profitable. Several studies show great efficiency when reducing bicarbonate solutions saturated with pure CO₂ gas to formate. However, those approaches don’t have a real application and our objective was to obtain similar results without pure CO₂ saturation. The method consists of electroreduction of the bicarbonate solution using bulk tin (Sn) as catalysts. Tin is a relatively cheap material that, according to previous studies performed in saturated bicarbonate solutions, shows a great selectivity towards formate. The ¹H NMR analysis of bicarbonate solutions after electroreduction show that, without pure CO₂ gas, the faradic efficiency is around 18% but almost 50% for saturated ones. The formate obtained could be used to power formate/formic acid fuel cells obtaining a battery-like system, with greater energy density than common lithium batteries, but electroreduction efficiency needs to be improved to make them competitive. Full article

This investigation’s primary purpose was to illustrate the cooling mechanism within a lithium titanate oxide lithium-ion battery pack through the experimental measurement of heat generation inside lithium titanate oxide batteries. Dielectric water/glycol (50/50), air and dielectric mineral oil were selected for the lithium titanate oxide battery pack’s cooling purpose. Different flow configurations were considered to study their thermal effects. Within the lithium-ion battery cells in the lithium titanate oxide battery pack, a time-dependent amount of heat generation, which operated as a volumetric heat source, was employed. It was assumed that the lithium-ion batteries within the battery pack had identical initial temperature conditions in all of the simulations. The lithium-ion battery pack was simulated by ANSYS to determine the temperature gradient of the cooling system and lithium-ion batteries. Simulation outcomes demonstrated that the lithium-ion battery pack’s temperature distributions could be remarkably influenced by the flow arrangement and fluid coolant type. Full article

Bisphenol A (BPA) is an endocrine-disrupting chemical (EDC) employed in industrial processes that causes adverse effects on the environment and human health. Sensitive and inexpensive methods to detect BPA are therefore needed. In this paper, we describe an electrochemical biosensor for detecting low levels of BPA using polymeric electrospun nanofibers of polyamide 6 (PA6) and poly(allylamine hydrochloride) (PAH) decorated with gold nanoparticles (AuNPs), namely, PA6/PAH@AuNPs, which were deposited onto a fluorine-doped tin oxide (FTO) substrate. The hybrid layer was excellent for the immobilization of tyrosinase (Tyr), which allowed an amperometric detection of BPA with a limit of detection of 0.011 μM in the concentration range from 0.05 to 20 μM. Detection was also possible in real water samples with recoveries in the range of 92–105%. The improved sensing performance is attributed to the combined effect of the large surface area and porosity of PA6/PAH nanofibers, the catalytic activity of AuNPs, and oxidoreductase ability of Tyr. These results provide a route for novel biosensing architectures to monitor BPA and other EDCs in water resources. Full article

In this study, we have evaluated the effect of potassium hydroxide (KOH) on the energy storage performance of metal-free carbon-based materials prepared from molasses. Molasses are a renewable-resource biomass and economical by-product of sugar refinement, used here as a carbon precursor. Two co-doped carbon materials using molasses were synthesized via a time and cost-efficient microwave carbonization process, with ammonium polyphosphate as a phosphorus and nitrogen doping agent. The phosphorus and nitrogen co-doped carbon (PNDC) samples were prepared in the presence and absence of a chemical activating agent (KOH), to study the role of chemical activation on PNDCs. Physical characterizations were performed to gain insight into the composition, pore size and topographical data of each material. Electrochemical characterization via cyclic voltammetry in 1 M sulfuric acid (H₂SO₄) as well as in 6 M KOH as electrolytes, revealed high current density and specific capacitance for the chemically activated material (PNDC2) compared to one without chemical activation (PNDC1). The capacitance value of 244 F/g in KOH electrolyte was obtained with PNDC2. It is concluded that addition of KOH prior to carbonization increases the surface functionality, which significantly enhances the electrochemical properties of the PNDC material such as current density, stability, and specific capacitance. Full article

Electrochemical immunosensors are affinity-based biosensors characterized by several useful features such as specificity, miniaturizability, low cost and simplicity, making them very interesting for many applications in several scientific fields. One of the significant issues in the design of electrochemical immunosensors is to increase the system’s sensitivity. Different strategies have been developed, one of the most common is the use of nanostructured materials as electrode materials, nanocarriers, electroactive or electrocatalytic nanotracers because of their abilities in signal amplification and biocompatibility. In this review, we will consider some of the most used nanostructures employed in the development of electrochemical immunosensors (e.g., metallic nanoparticles, graphene, carbon nanotubes) and many other still uncommon nanomaterials. Furthermore, their diagnostic applications in the last decade will be discussed, referring to two relevant issues of present-day: the detection of tumor markers and viruses. Full article

Nanocrystalline Ni-Co alloy deposits with grain sizes less than 30 nm were produced by electrodeposition with a direct current in a sulfamate bath. Surfaces of the Ni-Co alloy deposits showed granular morphology. The size of the granular particles and the Co content decreased when a lower current density was applied. Addition of NiBr₂ and a surface brightener (NSF-E) into the bath resulted in the grain refinement effect and an increase of Co content in the deposit. The grain size reached roughly 14 nm and 60 at.% of Co content in Ni-Co alloys electrodeposited with the bath containing the two additives. Ni-Co alloys obtained in this study showed higher microhardnesses than those of pure Ni and Co deposits prepared under the same condition, which revealed the solid solution strengthening effect. With a decrease in the grain size, the microhardness further increased, and this trend followed the Hall–Petch relationship well. The maximum microhardness value of 862.2 Hv was obtained owing to both the grain boundary and solid solution strengthening effects. Full article