Electrochem

Energy storage systems are becoming increasingly important as more renewable energy systems are integrated into the electrical (or power utility) grid. Low-cost and reliable energy storage is paramount if renewable energy systems are to be increasingly integrated into the power grid. Lead-acid batteries are widely used as energy storage for stationary renewable energy systems and agriculture due to their low cost, especially compared to lithium-ion batteries (LIB). However, lead-acid battery technology suffers from system degradation and a relatively short lifetime, largely due to its charging/discharging cycles. In the present study, we use Machine Learning methodology to estimate the battery degradation in an energy storage system. It uses two types of datasets: discharge condition and lead acid battery data. In the initial analysis, the Support Vector Regression (SVR) method with the RBF kernel showed poor results, with a low accuracy value of 0.0127 and RMSE 5377. On the other hand, the Long Short-Term Memory (LSTM) method demonstrated better estimation results with an RMSE value of 0.0688, which is relatively close to 0. Full article

Reported rate constants of charge transfer reactions (CTs) have ranged widely, depending on techniques and timescales. This fact can be attributed to the time-dependent double-layer capacitance (DLC), caused by solvent interactions such as hydrogen bonds. The time variation of the DLC necessarily affects the heterogeneous electrode kinetics. The delay by the solvation, being frequency dispersion, is incorporated into the CT kinetics in this report on the basis of the conventional reaction rate equations. It is different from the absolute rate theory. This report insists on a half value of the transfer coefficient owing to the segregation of the electrostatic energy from the chemical one. The rate equation here is akin to the Butler–Volmer one, except for the power law of the time caused by the delay of the DLC. The dipoles orient successively other dipoles in a group associated with the delay, which resembles that in the DLC. The delay suppresses the observed currents in the form of a negative capacitance. The above behavior was examined with a ferrocenyl derivative by ac impedance methods. The delay from diffusion control was attributed to the negative capacitance rather than the CT, even if the conventional DLC effect was corrected. Full article

TiO₂ composites with polypyrrole have gained attention for various applications; however, some reported results on the suitability of this heterojunction for photoelectrochemical water oxidation do not agree. In this sense, it is relevant to further study this material to clarify the role of polypyrrole in this system. Here, TiO₂ nanorods were grown on fluorine-doped tin oxide (FTO) substrates by a hydrothermal route; then, polypyrrole coatings were electrochemically synthetized on TiO₂ nanorods using a galvanostatic signal. The heterojunctions were characterized by different spectroscopic, microscopic, and electrochemical techniques. As a result, it was found that the polypyrrole underwent a rapid degradation process and that this process occurred independently of the amount of polymer deposited on the TiO₂, the illumination direction (back and front of the photoanode), and the type of light used (UV-Vis and Vis). In addition, from the measurements of the band positions of TiO₂ and the HOMO level of polypyrrole, it was shown that the TiO₂–polypyrrole heterojunction is not suitable for achieving the transfer of photogenerated holes to the electrolyte. These findings contribute to understanding the properties and interaction of two components of wide interest in materials science. Full article

In this study, ternary NiFeP coatings were fabricated on a copper substrate using a simple, fast, and cost-effective electroless deposition method. The coatings were named Ni₈₅Fe₄P₁₂, Ni₈₀Fe₈P₁₂, and Ni₇₅Fe₁₂P₁₂, indicating 4, 8, and 12 at % of Fe, respectively. The surface morphology and composition of the coatings were characterized using scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The activity of the prepared coatings was evaluated using the water-splitting reaction to determine the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in a 1 M KOH electrolyte solution. Electrochemical measurements were carried out in a temperature range from 25 °C to 55 °C. The HER and OER current density values increased by up to 2.58 and 2.13 times, respectively, with temperature increase compared to the result at 25 °C. All three coatings demonstrated activity in both reactions. Ni₈₅Fe₄P₁₂ exhibited the highest catalytic efficiency in the HER, with the overpotential of 340 mV at 10 mAcm⁻² and a Tafel slope of 61 mVdec⁻¹. In the OER, the efficiency of the NiFeP catalysts correlated with their Fe content. The overpotential was 412 mV for Ni₈₀Fe₈P₁₂ and 432 mV for Ni₇₅Fe₁₂P₁₂ at 10 mAcm⁻² with Tafel slopes of 96 and 91 mVdec⁻¹, respectively. This study underscores the critical influence of Fe content on the catalytic efficiency of NiFeP coatings, with reduced Fe content enhancing HER and increased Fe content benefits OER. Full article

The development of high-performance solid electrolytes is critical to advancing solid-state lithium-ion batteries (SSBs), with lithium lanthanum zirconium oxide (LLZO) emerging as a leading candidate due to its chemical stability and wide electrochemical window. In this study, we systematically investigated the effects of cation dopants, including aluminum (Al³⁺), tantalum (Ta⁵⁺), gallium (Ga³⁺), and rubidium (Rb⁺), on the structural, electronic, and ionic transport properties of LLZO using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. It appeared that, among all simulated results, Al-LLZO exhibits the highest ionic conductivity of 1.439 × 10⁻² S/cm with reduced activation energy of 0.138 eV, driven by enhanced lithium vacancy concentrations and preserved cubic-phase stability. Ta-LLZO follows, with a conductivity of 7.12 × 10⁻³ S/cm, while Ga-LLZO and Rb-LLZO provide moderate conductivity of 3.73 × 10⁻³ S/cm and 3.32 × 10⁻³ S/cm, respectively. Charge density analysis reveals that Al and Ta dopants facilitate smoother lithium-ion migration by minimizing electrostatic barriers. Furthermore, Al-LLZO demonstrates low electronic conductivity (1.72 × 10⁻⁸ S/cm) and favorable binding energy, mitigating dendrite formation risks. Comparative evaluations of radial distribution functions (RDFs) and XRD patterns confirm the structural integrity of doped systems. Overall, Al emerges as the most effective and economically viable dopant, optimizing LLZO for scalable, durable, and high-conductivity solid-state batteries. Full article

Metal–organic frameworks (MOFs) have characteristics such as a large specific surface area, distinct functional sites, and an adjustable pore size. However, the inherent low conductivity of MOFs significantly affects the charge transfer efficiency when they are used for electrocatalytic sensing. Combining MOFs with conductive materials can compensate for these deficiencies. For MOF/metal nanoparticle composites (e.g., composites with gold, silver, platinum, and bimetallic nanoparticles), the high electrical conductivity and catalytic activity of metal nanoparticles are utilized, and MOFs can inhibit the agglomeration of nanoparticles. MOF/carbon-based material composites integrate the high electrical conductivity and large specific surface area of carbon-based materials. MOF/conductive polymer composites offer good flexibility and tunability. MOF/multiple conductive material composites exhibit synergistic effects. Although MOF composites provide an ideal platform for electrocatalytic reactions, current research still suffers from several issues, including a lack of comparative studies, insufficient research on structure–property correlations, limited practical applications, and high synthesis costs. In the future, it is necessary to explore new synthetic pathways and seek; inexpensive alternative raw materials. Full article

The energy generated from renewable sources has an intermittent nature since solar irradiation and wind speed vary continuously. Hence, their energy should be stored to be utilized throughout their shortage. There are various forms of energy storage systems while the most widespread technique is the battery storage system since its cost is low compared to other techniques. Therefore, batteries are employed in several applications like power systems, electric vehicles, and smart grids. Due to the merits of the lithium-ion (Li-ion) battery, it is preferred over other kinds of batteries. However, the accuracy of the Li-ion battery model is essential for estimating the state of charge (SOC). Additionally, it is essential for consistent simulation and operation throughout various loading and charging conditions. Consequently, the determination of real battery model parameters is vital. An innovative application of the red-billed blue magpie optimizer (RBMO) for determining the model parameters and the SOC of the Li-ion battery is presented in this article. The Shepherd model parameters are determined using the suggested optimization algorithm. The RBMO-based modeling approach offers excellent execution in determining the parameters of the battery model. The suggested approach is compared to other programmed algorithms, namely dandelion optimizer, spider wasp optimizer, barnacles mating optimizer, and interior search algorithm. Moreover, the suggested RBMO is statistically evaluated using Kruskal–Wallis, ANOVA tables, Friedman rank, and Wilcoxon rank tests. Additionally, the Li-ion battery model estimated via the RBMO is validated under variable loading conditions. The fetched results revealed that the suggested approach achieved the least errors between the measured and estimated voltages compared to other approaches in two studied cases with values of 1.4951 × 10⁻⁴ and 2.66176 × 10⁻⁴. Full article

Electrocoagulation is rapidly gaining prominence in wastewater treatment due to its capabilities and less reliance on additional chemicals. While a lot of research efforts have been focused on the influence of the anode material, power supply, and reactor design, the contribution of the cathode to contaminant removal has been less explored. In this study, we investigated the performance of stainless steel (SS-304) and aluminium (Al-6061) electrodes in both similar and dissimilar configurations for a 120 min electrocoagulation treatment of spent machinery coolant. The anode–cathode configurations, including SS-SS, Al-Al, SS-Al and Al-SS, have been investigated. Additionally, we examined the effects of the initial pH and agitation methods on the process performance. Our findings indicated that the type of cathode could significantly affect the floc formation and contaminant removal. Notably, the combination of an Al anode and SS cathode (Al(A)-SS(C)) demonstrated a synergistic improvement in the Chemical Oxygen Demand (COD), with a removal of 84.3% within a short treatment time (<20 min). The final COD removal of 91.4% was achieved with a turbidity level close to 12 Nephelometric Turbidity Units (NTU). The Al anode readily released the Al ions and formed light flocs at the early stage of electrocoagulation, while the SS cathode generated heavy Fe hydroxides that mitigated the flotation effect. These results demonstrated the cathode’s significant contribution in electrocoagulation, leading to potential savings in the treatment time required. Full article

Laboratory data from in-cell tests at and near open circuit potentials (OCV) and ex-situ H₂O₂ vapor exposure tests are used to develop a fluoride emission rate (FER) model for a state-of-the-art 12-µm thin, low equivalent weight, long-chain perfluorosulfonic acid (PFSA) ionomer membrane that is mechanically reinforced with expanded PTFE and chemically stabilized with 2 mol% cerium as an anti-oxidant. The anode FER at OCV linearly correlates with O₂ crossover from the cathode and the high yield of H₂O₂ at anode potentials, as observed in rotating ring disk electrode (RRDE) studies. The cathode FER may be linked to the energetic formation of reactive hydroxyl radicals (·OH) from the decomposition of H₂O₂ produced as an intermediate in the two-electron ORR pathway at high cathode potentials. Both anode and cathode FERs are significantly enhanced at low relative humidity and high temperatures. The modeled FER is strongly influenced by the gradients in water activity and cerium concentration that develops in operating fuel cells. Membrane stability maps are constructed to illustrate the relationship between the cell voltage, temperature, and relative humidity for FER thresholds that define H₂ crossover failure by chemical degradation over a specified lifetime. Full article

An important class of analytes are volatile organic carbons (VOCs), particularly aliphatic primary alcohols. Here, we report the straightforward modification of a commercially available carbon monoxide sensor to detect a range of aliphatic primary alcohols at room temperature. The mass transport mechanisms governing the performance of the sensor were investigated using diffusion in multiple layers of the sensor to model the response to an abrupt change in analyte concentration. The sensor was shown to have a large capacitance because of the nanoparticulate nature of the platinum working electrode. It was also shown that the modified sensor had performance characteristics that were mainly determined by the condensation of the analyte during diffusion through the membrane pores. The sensor was capable of a quantitative amperometric response (sensitivity of approximately 2.2 µA/ppm), with a limit of detection (LoD) of 17 ppm methanol, 2 ppm ethanol, 3 ppm heptan-1-ol, and displayed selectivity towards different VOC functional groups (the sensor gives an amperometric response to primary alcohols within 10 s, but not to esters or carboxylic acids). Full article

The anodic stability of tungsten carbide (WC) and iron oxide with a spinel structure (Fe₃O₄) were compared against similar data for nanostructured, boron-doped diamond (BDD), and the benchmark Vulcan XC72 carbon, in view of their eventual application as alternative supports for the anion exchange membrane electrolyzer anode. To this end, metal oxide composites were prepared by the in situ autocombustion (ISAC) method, and the anodic behavior of materials (composites as well as supports alone) was investigated in 1 M NaOH electrolyte by the rotating ring–disc electrode method, which enables the separation oxygen evolution reaction and materials’ degradation currents. Among all supports, BDD has proven to be the most stable, while Vulcan XC72 is the least stable under the anodic polarization, with Fe₃O₄ and WC demonstrating intermediate behavior. The Co₃O₄-BDD, -Fe₃O₄, -WC, and -Vulcan composites prepared by the ISAC method were then tested as catalysts of the oxygen evolution reaction. The Co₃O₄-BDD and Co₃O₄-Fe₃O₄ composites appear to be competitive electrocatalysts for the OER in alkaline medium, showing activity comparable to the literature and higher support stability towards oxidation, either in cyclic voltammetry or chronoamperometry stability tests. On the contrary, WC- and Vulcan-based composites are prone to degradation. Full article

Highly dispersion antimony-doped tin oxide (ATO) nanoparticles were synthesized using a (220 °C, 2 L autoclave, medium scale) one-step hydrothermal method with Na₂SnO₃ and KSb(OH)₆ as precursors without a post-sintering process. The particle size reduces to a few nanometers with the increase in Sb content. The resulting various Sb-doping content ATO nanoparticles were coated onto a Ti foil substrate as an electrode for further electrochemical evaluation. The findings demonstrate that the prepared 30% Sb-doped ATO nanoparticles serve as a high-conductivity electrode material with excellent reversibility, substantial specific capacitance, and superior capacitance retention. The 30% ATO electrode exhibits the highest specific capacitance of 343.2 F g⁻¹ at a current density of 1 A g⁻¹ and maintains 93% of its capacitance after the first 10 charge/discharge cycles. The results indicate that ATO materials prepared by the hydrothermal method are promising candidates for supercapacitor electrodes. Full article

In recent years, protecting stainless steel from corrosion has become crucial, particularly in harsh environments. The present study focuses on improving the photocathodic corrosion resistance of 304 stainless steel (304SS) by fabricating TiO₂/CuO composite coatings using the spin coating technique with varying CuO weight percentages. Structural characterization through X-ray diffraction (XRD) confirmed the presence of the anatase phase of TiO₂ and the successful integration of CuO. Raman spectroscopy demonstrated redshifts in the TiO₂ characteristic peaks, suggesting changes in bond lengths attributed to CuO incorporation. These findings were further corroborated by Fourier-transform infrared (FTIR) spectroscopy. Surface characterization showed uniform, porous coatings with pore sizes ranging from 75 to 200 nm, which contributed to improved barrier properties. UV–visible diffuse reflectance spectroscopy (UV-DRS) demonstrated enhanced visible light absorption in the heterostructures. Mott–Schottky analysis confirmed improved charge carrier density and favorable band alignment, facilitating efficient charge separation. The electrochemical performance was evaluated in 3.5% NaCl solution under dark and light environments. The results demonstrated that the TiO₂/CuO heterostructure significantly enhanced electron transfer and suppressed electron-hole recombination, providing adequate photocathodic protection. Notably, under illumination, the TiO₂/CuO (0.005 g) coating achieved a corrosion potential of −255 mV vs SCE and reduced the corrosion current density to 0.460 × 10⁻⁶ mA cm⁻². These findings suggest that TiO₂/CuO coatings offer a promising, durable, and cost-effective solution for corrosion protection in industries such as oil, shipbuilding, and pipelines. Full article

Anode-free lithium-ion batteries offer a volumetric energy density approximately 60% higher than that of conventional lithium-ion cells. Despite this advantage, they often experience rapid capacity degradation and a limited cycle life. Optimizing electrolyte formulations—particularly through the use of specific additives, solvents, and lithium salts—is essential to improving these systems. This study explores electrolytes composed of fluorinated and carbonate-based solvents applied in anode-free lithium-ion cells featuring copper as the anode substrate and Li_1.05Ni_0.33Mn_0.33Co_0.33O₂ as the cathode. In the present work, the ionic conductivity of electrolytes was studied by impedance spectroscopy, and the electrochemical parameters of anode-free lithium-ion cells were compared using these electrolyte solutions: lithium difluoro(oxalato)borat (LIDFOB) salts were used in a mixture of solvents such as fluoroethylene carbonate (FEC) and dimethoxyethane (DME) in a ratio of 3:7 and in a mixture of propylene carbonate (PC) and dimethoxyethane in a ratio of 3:7. Enhanced performance was observed upon the substitution of conventional carbonates with fluorinated co-solvents. The findings suggest that LiDFOB is a thermostable salt, and its high conductivity contributes to the formation and stabilization of the interface of solid electrolytes. The results indicate that at low temperature conditions, a double salt should be used for lithium current sources, for example, 0.4 M LiDFOB and 0.6 M LiBF₄, as well as electrolyte additives such as fluoroethylene carbonate and lithium nitrate. Full article

This study presents the electrochemical detection of caffeic acid using an ester (Diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate)-modified carbon paste electrode (EMCPE). Caffeic acid, a naturally occurring hydroxycinnamic acid with antioxidant properties, was investigated due to its significance in food products and its potential health benefits. The modified electrode demonstrated enhanced sensitivity and selectivity for caffeic acid detection. Voltammetric methods were applied to evaluate the electrode performance. Results indicated that EMCPE has improved electron transfer kinetics and a lower detection limit compared unmodified electrode. Detection and quantification thresholds (LOD and LOQ) were found to be $3.12\times {10}^{-6}$ M and $1.04\times {10}^{-3}$ M. Density functional theory used to understand the electron transfer properties of Diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate. The study highlights the potential of EMCPE as a reliable and cost-effective sensor to quantify caffeic acid across different sample matrices. Full article

This study presents a comprehensive bibliometric analysis of scientific publications on electrochemical etching and electrochemical deposition from 1970 to 2023. Using the Science Citation Index Expanded (SCIE) database, we analysed 5166 publications on electrochemical etching and, 30,759 publications on electrochemical deposition. The analysis reveals distinct yet interconnected research landscapes for these two techniques. Electrochemical etching research has focused on themes such as porous silicon, photoluminescence, and applications in photonics, while electrochemical deposition research has centred on energy storage, catalysis, and biosensing applications. Keyword co-occurrence analysis illustrates the progression from fundamental studies to specialised applications in both fields. This study highlights the importance of international collaboration and provides insights into the historical and contemporary advancements in electrochemical methods for nanomaterial synthesis. The findings underscore the complementary nature of electrochemical etching and deposition, driving innovation and offering new opportunities in materials science and technology. Full article

We demonstrate the reconstruction of battery electrochemical impedance spectroscopy (EIS) curves from time-domain pulse testing and the distribution of relaxation times (DRT) analysis. In the proposed approach, the DRT directly utilizes measured current data instead of simulated current patterns, thereby enhancing robustness against current variations and data anomalies. The method is demonstrated with a simulation, a single cylindrical battery cell experiment, and an experimental EIS of a completely assembled module of 448 cells. For the 3.7 kWh battery module, we applied a transient current pulse and analyzed the dynamic voltage responses. The EIS curves were reconstructed with DRT and compared to experiments across different states of charge (SoC). The experimental EIS data were corrected by a multistep calibration workflow in a frequency range from 50 mHz to 1 kHz, achieving error corrections of up to 80% at 1 kHz. The reconstructed impedances from the pulse test data are in good agreement with the EIS experiments in a broad frequency range, delivering relevant electrochemical information including the ohmic resistance and dynamic time constants of a battery module and its corresponding submodules. With the proposed workflow, rapid pulse tests can be used for extracting electrochemical information faster than standard EIS, with a 67% reduction in measurement time. This time-domain pulsing approach provides an alternative to EIS characterization, making it particularly valuable for battery monitoring, the classification of battery packs upon their return to the manufacturer, second-life applications, and recycling. Full article

Cobalt electrochemical deposition, with its bottom–up growth properties, is a core technology for creating metal interconnects. Additives are crucial during electrodeposition to control the quality of deposits by adsorbing onto the Co surface. The functional groups of additive molecules are the key to tailoring the adsorption behavior. This study focuses on heteroaromatic thiol additives, including 2-mercaptobenzimidazole (MBI), 2-mercapto-5-benzimidazolesulfonic acid sodium salt dehydrate (MBIS), and 2-mercaptobenzoxazole (MBO). Cyclic voltammetry, chronopotentiometry, quantum chemical calculations, and characterization tests were employed to investigate the adsorption behavior of additive molecules with different functional groups on cobalt. The results indicate that the inhibitory strength of the three additives on electrodeposition follows the following order: MBI > MBIS > MBO. The strong inhibitory effect of MBI primarily stems from the adsorption of the thiol group, the pyridine-like nitrogen in the heterocycle, and the benzene ring. MBIS exhibits reduced inhibitory capability due to the combined effects of the sulfonic acid group and hydrolysis ionization. MBO, with the introduction of an oxygen atom in the heterocycle, shows the weakest adsorption and inhibitory capability among the three. Full article

The manufacturing of integrated circuits involves multiple steps of chemical mechanical planarization (CMP) involving different materials. Mitigating CMP-induced defects is a main requirement of all CMP schemes. In this context, controlling galvanic corrosion is a particularly challenging task for planarizing device structures involving contact regions of different metals with dissimilar levels of corrosivity. Since galvanic corrosion occurs in the reactive environment of CMP slurries, an essential aspect of slurry engineering for metal CMP is to control the surface chemistries responsible for these bimetallic effects. Using a CMP system based on copper and cobalt (used in interconnects for wiring and blocking copper diffusion, respectively), the present work explores certain theoretical and experimental aspects of evaluating and controlling galvanic corrosion in barrier CMP. The limitations of conventional electrochemical tests for studying CMP-related galvanic corrosion are examined, and a tribo-electrochemical method for investigating these systems is demonstrated. Alkaline CMP slurries based on sodium percarbonate are used to planarize both Co and Cu samples. Galvanic corrosion of Co is controlled by using the metal-selective complex forming functions of malonic acid at the Co and Cu sample surfaces. A commonly used corrosion inhibitor, benzotriazole, is employed to further reduce the galvanic effects. Full article