Electrochem

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

In the past ten years, many coal mines have encountered the problem of a premature failure of anchor rod materials. Through field investigation and laboratory research, it was found that the premature failure of these bolt materials is mostly caused by mine water corrosion. In this paper, a Zn-Y₂O₃-Al₂O₃ composite coating was prepared by an electrodeposition method for the corrosion protection of underground anchors. Through the single-factor experiment method, the co-deposition process of Zn²⁺ nano-Y₂O₃ and nano-Al₂O₃ particles was studied. Microhardness was used as the index to determine the optimum preparation process for the composite coatings. Combined with FSEM and XRD tests, the results showed that the synergistic effect of nano-Y₂O₃ and nano-Al₂O₃ particles made the coating grain refined and reduced the coating defects. The hardness of the coating increased from 98.7 Hv to 347.9 Hv, and the hardness and wear resistance of the coating were improved. The hydrophobicity of the Zn-Y₂O₃-Al₂O₃ composite coating was improved, and its static contact angle was 93.28°. The corrosion resistance of the composite coating was studied through electrochemical impedance spectroscopy, the Tafel curve, corrosion morphology, and weight loss. Under the synergistic effect of nano-Y₂O₃ and nano-Al₂O₃ particles, the self-corrosion current density decreased from 4.21 × 10⁻⁴ A/cm² to 1.06 × 10⁻⁵ A/cm², which confirmed that the Zn-Y₂O₃-Al₂O₃ composite coating had better corrosion resistance and durability. After soaking in mine water for 63 days, the Zn-Y₂O₃-Al₂O₃ composite coating had no obvious shedding on the surface and was well preserved. The practical application results show that it has excellent corrosion resistance and durability. The Zn-Y₂O₃-Al₂O₃ nano-composite coating material has significant potential advantages in the field of corrosion resistance of underground anchor rods. Full article

Structural batteries, also known as “massless batteries”, integrate energy storage directly into load-bearing materials, offering a transformative alternative to traditional Li-ion batteries. Unlike conventional systems that serve only as energy storage devices, structural batteries replace passive structural components, reducing overall weight while providing mechanical reinforcement. However, achieving uniform and efficient coatings of active materials on carbon fibers remains a major challenge, limiting their scalability and electrochemical performance. This study investigates ultrasonic spray coating as a precise and scalable technique for fabricating composite cathodes in structural batteries. Using a computer-controlled ultrasonic nozzle, this method ensures uniform deposition with minimal material waste while maintaining the mechanical integrity of carbon fibers. Compared to traditional techniques such as electrophoretic deposition, vacuum bag hot plate processing, and dip-coating, ultrasonic spray coating achieved superior coating consistency and reproducibility. Electrochemical testing revealed a specific capacity of 100 mAh/g_LFP with 80% retention for more than 350 cycles at 0.5 C, demonstrating its potential as a viable coating solution. While structural batteries are not yet commercially viable, these findings represent a step toward their practical implementation. Further research and optimization will be essential in advancing this technology for next-generation aerospace and transportation applications. Full article

The aim of this study was to enhance and maintain bioelectricity generation from distillery spent wash using a microbial fuel cell (MFC). Electrode materials play a critical role in the generation of bioelectricity in MFCs. Utilizing double oxidant-treated carbon felts in MFC applications increased current density to 749.56 mA/m² and increased peak power density to 125.23 mW/m². Electrochemical impedance spectroscopy (EIS) analysis further verified the improved electrocatalytic activity observed in the oxidized carbon felt, consistent with the findings from cyclic voltammetry (CV) and polarization curves, thereby confirming the enhanced performance of the oxidized carbon felt electrode. Overall, the study highlights the significance of electrode morphology and surface modifications in influencing microbial adhesion, electron transport, and the overall efficiency of fuel cells using distillery spent wash as a substrate. Full article

This review reveals the parameters of next-generation fuel cells for portable applications such as cellular phones, laptops, automobiles, etc. Disputes over issues such as design, fluid dynamics, channel dimensions, thermal management, and water management must be overcome for practical applications. We examine techniques such as microfabrication, material selection for membranes and electrodes, and integration challenges in small-scale devices, in addition to issues like methanol crossover, low efficiency at high methanol concentrations, thermal management, and the cost of materials. The advancements in micro-DMFC stacks and prototype developments are presented, and the challenges relating to micro-DMFCs are also identified and reviewed in detail. The challenges in the development of micro-DMFC applications are also presented, including the need for a better understanding of the anode and cathode catalyst structure and for high catalyst loadings in oxidation-and-reduction reactions. Also, a comprehensive and highly valuable database for advancing innovations and enhancing the understanding of micro-DMFCs for potential applications is provided. Full article

The preparation and properties of Nafion–TMS (Nafion–trimethylsilyl) and Nafion–TMS–Ru²⁺-complex modified GC electrodes are reported for the electrochemical oxidation reaction of adrenaline (AD). The structure of Nafion–TMS was studied by atomic force microscopy. The incorporation of [Ru(bpy)₃]²⁺ and [Ru(phen)₃]²⁺ complexes into Nafion–TMS was investigated by UV-vis spectroscopy, providing information about the interaction of the modified Nafion–TMS–Ru²⁺-complex composite. According to electrochemical studies, the electrodes modified with this composite polymer showed a faster electron transfer and greatly improved kinetics for the redox reaction of AD in standard solutions when compared to bare and Nafion–TMS modified electrodes. The oxidation current increased linearly with adrenaline concentration in the range from 1 to 20 mM and 1 to 100 mM for Nafion–TMS and the modified Nafion–TMS–Ru²⁺ complex, respectively. A strong pH dependence on the electroanalytical parameters was found for adrenaline detection, indicating that electron transfer reaction occurs in tandem with proton transfer. Full article

In a plant microbial fuel cell (P-MFC), the plant provides the fuel in the form of exudates secreted by the roots, which are oxidised by electroactive bacteria. The immature plant is hampered by low energy yields. Several factors may explain this situation, including the low open-circuit voltage of the plant cell. This is a function of the development of the biofilm formed by the electroactive bacteria on the surface of the anode, in relation to the availability of the exudates produced by the roots. In order to exploit the fertilising role of biochars, a plant cell was developed from C. citratus and grown in a medium to which 5% by mass of coconut shell biochar had been added. Its effect was studied as well as the distance between the electrodes. The potential of Cymbopogon citratus was also evaluated. Three samples without biochar, with inter-electrode distances of 2, 5 and 7 cm, respectively, identified as SCS2, SCS5 and SCS7, and three with the addition of 5 % biochar, with the same inter-electrode distance values, identified as S2, S5 and S7, were prepared. Open-circuit voltage (OCV) measurements were taken at 6 a.m., 1 p.m. and 8 p.m. The results showed that all the samples had high open-circuit voltage values at 1 p.m. Samples containing 5% biochar had open-circuit voltages increased by 16 %, 8.94% and 5.78%, respectively, for inter-electrode distances of 2, 5 and 7 cm compared with those containing no biochar. Furthermore, the highest open-circuit voltage values were obtained for all samples with C. citratus at an inter-electrode distance of 5 cm. The maximum power output of the PMFC with C. citratus in this study was 75.8 mW/m², which is much higher than the power output of PMFCs in recent studies. Full article

In this study, we developed lithium–sulfur rechargeable batteries using chemically modified thermoplastic sulfur polymers as cathode active materials, aiming to effectively utilize surplus sulfur resources. The resulting high-sulfur-content resins exhibited self-healing properties, extensibility, and adhesiveness. By leveraging its high solubility in specific organic solvents, we successfully introduced sulfur-based compounds into porous carbon via vacuum impregnation using a solution, rather than conventional thermal impregnation. Charge–discharge measurements of lithium–sulfur (Li-S) secondary batteries assembled with this more uniform composite cathode, compared to those using elemental sulfur, demonstrated an increased discharge capacity in the initial cycles and at higher rates. Full article

The electrocatalytic reduction of nitric oxide and nitrogen dioxide (NOx) remains a significant challenge due to the need for stable, efficient, and cost-effective materials. This study presents a novel support system for NOx reduction in alkaline media, composed of ZrO₂-WO₃-C (ZWC), synthesized via coprecipitation. Platinum nanoparticles (10 wt.%) were loaded onto ZWC and Vulcan carbon support, using similar methods for comparison. Comprehensive physicochemical and electrochemical analyses (N₂ physisorption, XRD, XPS, SEM, TEM, and cyclic and linear voltammetry) revealed that PtZWC outperformed PtC and commercial PtEtek in NOx electrocatalysis. Notably, PtZWC exhibited the highest total electric charge for NOx reduction. At the same time, the hydrogen evolution reaction (HER) was shifted to more negative cathodic potentials, indicating reduced hydrogen coverage and a modified dissociative Tafel mechanism on platinum. Additionally, the combination of WO₃ and ZrO₂ in ZWC enhanced electron transfer and suppressed HER by reducing NO and hydrogen atom adsorption competition. While the incorporation of WO₃ and ZrO₂ lowered the surface area to 96 m²/g, it significantly improved pore properties, facilitating better Pt nanoparticle dispersion (3.06 ± 0.85 nm, as confirmed by SEM and TEM). XRD analysis identified graphite and Pt phases, with monoclinic WO₃ broadening PtZWC peaks (20–25°). At the same time, XPS confirmed oxidation states of Pt, W, and Zr and tungsten-related oxygen vacancies, ensuring chemical stability and enhanced catalytic activity. Full article

Sodium-ion batteries (SIBs) have garnered significant attention as a cost-effective and sustainable alternative to lithium-ion batteries (LIBs) due to the abundance and eco-friendly extraction of sodium. Despite the larger ionic radius and heavier mass of sodium ions, SIBs are ideal for large-scale applications, such as grid energy storage and electric vehicles, where cost and resource availability outweigh the constraints of size and weight. A critical component in SIBs is the electrolyte, which governs specific capacity, energy density, and battery lifespan by enabling ion transport between electrodes. Among various electrolytes, composite polymer electrolytes (CPEs) stand out for their non-leakage and non-flammable nature and tunable physicochemical properties. The incorporation of NASICON (Na Super Ionic CONductor) fillers into polymer matrices has shown transformative potential in enhancing SIB performance. NASICON fillers improve ionic conductivity by forming continuous ion conduction pathways and reduce polymer matrix crystallinity, thereby facilitating higher sodium-ion mobility. Additionally, these fillers enhance the mechanical properties and electrochemical performance of CPEs. Hence, this review focuses on the pivotal roles of NASICON fillers in optimizing the properties of CPEs, including ionic conductivity, structural integrity, and electrochemical stability. The mechanisms underlying sodium-ion transport facilitated by NASICON fillers in CPE will be explored, with emphasis on the influence of filler morphology and composition on electrochemical properties. By scrutinizing the recent findings, this review underscores the potential of NASICON-based composite polymer electrolytes as appropriate material for the development of advanced sodium-ion batteries. Full article

Sodium–ion batteries are emerging as strong competition to lithium–ion batteries in certain market sections. While these cells do not use critical raw materials, they still feature a liquid electrolyte with all its inherent safety issues, like high flammability and toxicity. Alternative concepts like oxide-ceramic-based all-solid-state batteries feature the highest possible safety while still maintaining competitive electrochemical performance. However, production technologies are still in their infancy, especially for Na all-solid-state batteries, and need to be urgently developed to enable solid-state-battery technology using only abundant raw materials. In this study, the additive-free production of freestanding, undoped NaSICON separators via tape-casting is demonstrated, having an extremely high total Na-ion conductivity of up to 2.44 mS·cm⁻¹ at room temperature. Nevertheless, a strong influence of sample thickness on phase purity as well as electrochemical performance is uncovered. Additionally, the effect of self-coating of NaSICON during high-temperature treatment was evaluated as a function of thickness. While advantageous for increasing the stability against Na-metal anodes, detrimental consequences are identified when separator thickness is reduced to industrially relevant values and mitigation measures are postulated. Full article

The electrochemical properties of the hydrophobic room-temperature ionic liquid 1-propyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide (PMMIm(TFSI)) were investigated, for the first time, using an electrochemical double-layer capacitor-mimicking cell containing two identical-sized micro–mesoporous molybdenum carbide-derived carbon electrodes (MMP-C(Mo₂C)), by applying cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Surprisingly, despite the substitution of the slightly acidic hydrogen atom with a methyl group at the carbon atom located between two nitrogen atoms in the imidazolium cation, the EIS and CV measurements demonstrated that PMMIm(TFSI) began to decompose electrochemically at the same cell potential (ΔE) as 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIm(BF₄)), specifically at ΔE = 2.75 V. However, the CV and EIS data indicated that PMMIm(TFSI) decomposed with a significantly lower intensity than EMIm(BF₄). Therefore, we believe that the use of PMMIm(TFSI) as the electrolyte will enable the construction of safer supercapacitors that can tolerate short periods of over-polarization up to ΔE = 4.0 V. However, when the ΔE ≤ 3.2 V was applied, EMIm(BF₄) offered higher maximum power compared to PMMIm(TFSI). We found that the calculated maximum gravimetric power precisely describes the maximum ΔE applicable for a supercapacitor candidate. Full article

Due to their diverse properties and functionalities, cost-effective transition metal-based nanomaterials have been rigorously studied for electrochemical applications. Ultrathin nanosheets have been identified as the most effective electrodes for catalyzing water-splitting reactions in both acidic and alkaline environments. Here, we reported ZnWO₄, a member of the tungstate family, as an effective electrocatalyst for promoting the electrochemical hydrogen evolution reaction. The Zn⁺²-stabilized tungstate showed a remarkable cathodic reaction during the water-splitting reaction with low overpotential (136 mV at 10 mA cm⁻²) and small HER kinetics (Tafel Slope = 75.3 mV dec⁻¹) and long-term cyclic durability. The high-valence tungsten stabilized with divalent Zn⁺² promotes electron transfer during the reaction, making it an advanced electrocatalyst for green hydrogen production. Full article

There is a high demand for nickel hydroxide as an engineering material used in the positive electrode of nickel metal hydride (Ni-MH) rechargeable batteries. These batteries are extensively used in various small instruments, disposable batteries, and electric vehicles. The structure of nickel hydroxide significantly influences the discharge capacity and energy density, key properties of Ni-MH batteries, and this structure is primarily determined by the synthesis method used. In this study, nickel hydroxide was synthesized using an electrochemical precipitation method, with current density acting as a parameter to control the desired phase of the product, whether α-nickel hydroxide, β-nickel hydroxide, or a combination of both. At a current density of 50 A/m², the synthesized nickel hydroxide demonstrated a smaller particle size and a superior discharge electrochemical property in comparison to that generated at 500 A/m². The effect of agitation in catholyte was also investigated to examine the change in discharge property of the precipitated material. The product synthesized at 500 A/m² from an agitated catholyte exhibited a tap density of 1.24 g/cc and an improved discharge capacity of 254 mAh per gram of Ni(OH)₂. Full article

This research investigates the corrosion behavior of copper (Cu) through a comprehensive analysis of both plain and nanoporous Cu thin films. A combination of weight-loss methods for quantitative analysis, along with polarization testing and scanning electron microscopy, is employed for both quantitative and qualitative assessments of Cu corrosion dynamics. The corrosion mechanisms in chloride and nitrate solutions are compared, with an additional discussion on the influence of atmospheric oxygen (O₂). The results demonstrate that chloride ions and the presence of O₂ create the most severe corrosion conditions, while the concentration of salts has a relatively minor effect on the corrosion behavior. Notably, the comparative study reveals that nanoporous Cu exhibits a greater corrosion tendency, as indicated by more negative corrosion potentials. However, its corrosion rates are lower than those of plain Cu, as determined by corrosion current density measurements. Full article