Electrochimica Acta最新文献

{"title":"Performance and stability of PtCo alloy catalysts in high-temperature polymer electrolyte membrane fuel cells","authors":"V. Domin, M. Prokop, T. Bystron, M. Gatalo, L. Pavko, N. Hodnik, B.F. Gomes, C.M.S. Lobo, C.E. Hartwig, C. Roth, M. Paidar, K. Bouzek","doi":"10.1016/j.electacta.2025.146707","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146707","url":null,"abstract":"High-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) suffer from fast catalyst degradation and catalyst poisoning by phosphate anions. Their performance can be tuned by alloying Pt with a less noble metal and by choosing an appropriate catalyst support and preparation method. To address this, we investigate the performance of two novel PtCo intermetallic alloy catalysts supported either on carbon black or reduced graphene oxide (rGO), prepared by double passivation galvanic displacement method, appropriate thermal annealing and <em>ex situ</em> chemical activation. The catalysts were used on the cathode and/or anode of a single cell (H₂/O₂, 180°C, 144 h) to shed light on the Co lifecycle in HT-PEMFCs. <em>I</em>-<em>U</em> curves as well as electrochemical impedance spectroscopy showed that their use on the cathode improved cell performance, partly also due to Co dissolution, providing higher surface area and more active sites. On the other hand, when they were used on the anode and on both electrodes, the cell performance was marked by severely inhibited mass transport due to Co phosphate formation. XRF and XAS showed that regardless of where a PtCo catalyst is used, Co at least partly dissolves and is transported to the other electrode, affecting the cell performance.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"27 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrodeposition of metals on silicon for enhanced silicon nanowires (NWs) Fabrication via metal assisted chemical etching (MACE)","authors":"Giulio Pappaianni ,&nbsp;Francesco Visconti ,&nbsp;Francesco Montanari ,&nbsp;Marco Bonechi ,&nbsp;Claudio Fontanesi ,&nbsp;Marco Pagliai ,&nbsp;Walter Giurlani ,&nbsp;Massimo Innocenti","doi":"10.1016/j.electacta.2025.146705","DOIUrl":"10.1016/j.electacta.2025.146705","url":null,"abstract":"<div><div>In this study, gold nanoparticles were electrodeposited onto a silicon substrate and evaluated for their potential use in metal-assisted chemical etching (MACE). Electrodeposition offers high scalability while reducing material waste compared to vapor-phase deposition techniques, and provides greater control than wet electroless deposition. Various deposition conditions including the oxidation state of the gold salt, pH, reduction potential, and deposition time were tested to determine the optimal combination for producing thin, homogeneous silicon nanowires (NWs) via MACE. The resulting deposits and NWs were thoroughly characterized using a scanning electron microscope (SEM). This approach could open new possibilities for developing smaller, higher-performance sensors and high-surface-area electrodes, particularly when Si NWs are decorated with metals or other chemical species.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"535 ","pages":"Article 146705"},"PeriodicalIF":5.5,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrical conductivity of lead silicate slags with iron oxide in air","authors":"Pieter-Jan Boeykens ,&nbsp;Amy Van den Bulck ,&nbsp;Lennart Scheunis ,&nbsp;Inge Bellemans ,&nbsp;Kim Verbeken","doi":"10.1016/j.electacta.2025.146704","DOIUrl":"10.1016/j.electacta.2025.146704","url":null,"abstract":"<div><div>This study investigates the electrical conductivity and conduction mechanisms of lead silicate slags. The primary objectives were to assess the applicability of stepped potential chronoamperometry (SPC) measurements in systems with volatile components like PbO and to understand the contribution of Fe³⁺ with respect to the ionic conductivity. Experiments were carried out in a ternary SiO₂ – PbO – FeO_1.5 system (max 10 mol % FeO_1.5) between 1000 °C and 1300 °C under air to ensure that the iron cations were predominantly Fe³⁺. From the SPC measurements, it was found that the current was predominantly carried via ions. The exact electronic transference number could however not be determined as it is possible that faradaic reactions still take place at the slag-electrode interface during the SPC measurement. Regarding the total/ionic conductivity, it is found that substituting PbO and SiO₂ for FeO_1.5 results in respectively a significant decrease and increase of the slags electrical conductivity. The activation energy on the other hand was found to increase for PbO substitution, whereas it remained constant for SiO₂ substitution. This was linked to the type, number and proximity of easy cation hopping sites within the slag.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"535 ","pages":"Article 146704"},"PeriodicalIF":5.5,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A simple, sensitive and wide range electrochemical sensor for tinidazole detection in water, food and pharmaceutical samples","authors":"Arun Warrier ,&nbsp;Pooja Das Manjulabhai ,&nbsp;Dhanya Gangadharan ,&nbsp;Jeethu Raveendran","doi":"10.1016/j.electacta.2025.146678","DOIUrl":"10.1016/j.electacta.2025.146678","url":null,"abstract":"<div><div>An electroanalytical method has been developed for the detection of tinidazole (TNZ) based on electrochemical reduction with a simple and inexpensive self-made screen-printed electrode (SPE). The present study has optimized the analytical method regarding the technique and electrochemical parameters using Differential Pulse Voltammetry (DPV). The calibration curve was obtained with a linear range of 20 μM - 2.7 mM range, with a limit of detection (LOD) and limit of quantification (LOQ) of 0.024 μM and 0.08 μM, respectively. The developed sensor is highly selective with no interference in the presence of amoxicillin, ciprofloxacin, paracetamol, glucose, and uric acid. The study showed excellent results for the analysis of tinidazole in food, water, and other environmental samples which is proved by the excellent recovery of tinidazole in water, honey, milk, and other real samples. The sensor also possessed good repeatability and reproducibility which proved to be a valuable tool for the detection of tinidazole in environment samples and also its application in diagnostics.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"536 ","pages":"Article 146678"},"PeriodicalIF":5.5,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unleashing the power of MnMoO4/rGO nanocomposite towards the electrochemical aptasensing of neurotoxic pesticide fenitrothion","authors":"Jeyaraj Vinoth Kumar ,&nbsp;Ragi Adham Elkaffas ,&nbsp;Shimaa Eissa","doi":"10.1016/j.electacta.2025.146708","DOIUrl":"10.1016/j.electacta.2025.146708","url":null,"abstract":"<div><div>This work presents a manganese molybdate/reduced graphene oxide (MnMoO₄/rGO) nanocomposite as the foundation for an advanced aptamer-based electrochemical biosensor for fenitrothion (FNT), a neurotoxic organophosphate pesticide. Utilizing a modified hydrothermal synthesis method with citric acid as a surfactant, MnMoO₄ was engineered into a hexagonal morphology that, when combined with reduced graphene oxide, creates a synergistic nanostructure with enhanced conductivity, electron transfer, and active site exposure. Extensive characterization was conducted using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) to confirm the successful synthesis of the composite. The prepared composite demonstrated superior electrochemical properties compared to MnMoO₄ synthesized through urea-assisted hydrothermal and co-precipitation methods. Functionalized with a specific DNA aptamer, the MnMoO₄/rGO-based aptasensor with an optimized ratio demonstrated remarkable sensitivity with an ultra-low detection limit of 0.3 pg/mL with wide linear ranges of 1 pg/mL to 100 µg/mL. Its high selectivity against other pesticides such as malathion, edifenphos, and imidacloprid, low relative standard deviation (RSD) values, and robust stability underscore its reliability and practicality. Successfully applied to real-world matrices such as wastewater, tap water, and rice extracts, this MnMoO₄/rGO-based aptasensor sets a benchmark in electrochemical biosensing for environmental and food safety applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"536 ","pages":"Article 146708"},"PeriodicalIF":5.5,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A comprehensive study of highly concentrated Lithium‑ion aqueous electrolytes: from structural characterizations to electrochemical properties","authors":"Léa Flores ,&nbsp;Jean‑Frédéric Martin ,&nbsp;Pierre Toudret ,&nbsp;Pierre‑Alain Bayle ,&nbsp;Sébastien Martinet","doi":"10.1016/j.electacta.2025.146680","DOIUrl":"10.1016/j.electacta.2025.146680","url":null,"abstract":"<div><div>Due to their scarce and expensive components, lithium‑ion batteries raise safety and cost concerns. Aiming for less toxic and cheaper batteries, aqueous electrolytes have emerged as a good alternative. To overcome their narrow electrochemical stability window, highly concentrated electrolytes have shown promising properties in reducing water reactivity. However, the lithium salts most commonly used in these electrolytes contain fluorinated organic anions, which have greater environmental and cost impacts when used in large amounts. Some low‑cost and more environmentally‑friendly salts started to emerge in aqueous electrolytes for battery and supercapacitor applications. In the present work, a comparative study between a low‑cost and highly concentrated lithium nitrate (LiNO₃) based electrolyte and an electrolyte using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt as a reference was conducted. Electrochemical measurements reveal that LiNO₃‑based electrolytes have a higher ionic conductivity but a narrower electrochemical stability window than LiTFSI‑based ones. Infrared spectroscopy, small‑angle X‑ray scattering and wide‑angle X‑ray scattering characterisations, coupled with self‑diffusion and viscosity measurements, shed light on the lack of structure formation in LiNO₃‑based electrolytes compared to LiTFSI‑based ones which have well‑organised domains. It demonstrates that LiNO₃ used alone in an aqueous electrolyte does not disrupt the network of water molecules and, therefore, does not reduce their reactivity. This study also proposes a systematic approach to evaluate salts or electrolyte formulations for application in low-cost aqueous batteries. By combining various characterisation techniques, it provides a framework to determine whether a given composition meets the essential criteria for widening the electrochemical stability window of aqueous electrolytes.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"536 ","pages":"Article 146680"},"PeriodicalIF":5.5,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-performance bifunctional electrochromic-supercapacitor devices based on indole derivative copolymerized with 3,4-ethylenedioxythiophene","authors":"Shadi Hosseini ,&nbsp;Yasemin Arslan Udum ,&nbsp;Levent Toppare","doi":"10.1016/j.electacta.2025.146667","DOIUrl":"10.1016/j.electacta.2025.146667","url":null,"abstract":"<div><div>The integration of energy storage and electrochromic functionalities into a single device holds great promise for smart windows, displays, and energy-efficient systems. This study presents the first bifunctional electrochromic supercapacitor device (ECSCD) based on an indole-7-carboxylic acid (IN7Ca) and 3,4-ethylenedioxythiophene (EDOT) copolymer, synthesized via electropolymerization. Unlike conventional single-material systems, this work leverages a novel asymmetric design (PIN7Ca anode/P(EDOT-co-IN7Ca) cathode) to simultaneously achieve record performance in both optical and energy storage metrics. The electrochromic and supercapacitor properties of the homopolymer (PIN7Ca), copolymer (P(EDOT-co-IN7Ca)), and PEDOT are systematically investigated. The copolymer demonstrates unprecedented optical transmittance, faster switching (1.8 s), and enhanced electrochromic performance due to the incorporation of EDOT. Its improved capacitive behavior and &gt;90 % cycling stability after 2000 cycles arise from the synergistic combination of IN7Ca’s redox activity and EDOT’s electrochromic stability. An asymmetric ECSCD achieves a record electrochromic contrast (ΔT = 47 %) among solution-processed devices, alongside a high specific capacitance (1.9 mF/cm² at 0.01 mA/cm²) that surpasses recent PEDOT- and PANI-based systems by &gt;30 %. These results highlight copolymerization as an effective strategy for designing multifunctional materials with benchmark performance. This approach establishes new design principles for high-performance ECSCDs, supporting their integration into next-generation smart and sustainable technologies.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"536 ","pages":"Article 146667"},"PeriodicalIF":5.5,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Parameter sensitivity analysis and calibration of a discrete element model for optimizing all-solid-state-battery cathode microstructures","authors":"Ali Mohammad Bazzoun ,&nbsp;Javid Piruzjam ,&nbsp;Steffen Hink ,&nbsp;Lukas Rubacek ,&nbsp;Alexander Fill ,&nbsp;Thomas Carraro ,&nbsp;Kai Peter Birke","doi":"10.1016/j.electacta.2025.146536","DOIUrl":"10.1016/j.electacta.2025.146536","url":null,"abstract":"<div><div>This study develops and evaluates a Discrete Element Method (DEM) model designed to simulate the produced cathode composite microstructures during uniaxial cold-pressing of All-Solid-State-Battery (ASSB) electrodes. The research primarily investigates how variations in model input parameters – such as particle size distribution, interparticle friction, and mechanical properties – affect critical performance indicators, including cathode active material (CAM) utilization (<span><math><msub><mrow><mi>θ</mi></mrow><mrow><mtext>CAM</mtext></mrow></msub></math></span>), packing behavior, porosity (<span><math><mi>ϵ</mi></math></span>), and solid electrolyte (SE) utilization (<span><math><msub><mrow><mi>θ</mi></mrow><mrow><mtext>SE</mtext></mrow></msub></math></span>), contributing to network formation and ionic percolation within DEM-generated composite cathodes. A comprehensive parameter sensitivity analysis highlights that frictional interactions are the most influential factors governing particle connectivity, percolation, and porosity, especially at higher CAM loadings (<span><math><msub><mrow><mi>f</mi></mrow><mrow><mtext>CAM</mtext></mrow></msub></math></span>). In addition to simulations, experimental measurements were performed to validate the DEM model and further analyze the cathode behavior under varying conditions. Both experimental and simulation results consistently demonstrate that increasing uniaxial pressure enhances discharge capacity by improving particle connectivity. However, while the DEM model exhibits high accuracy at lower <span><math><msub><mrow><mi>f</mi></mrow><mrow><mtext>CAM</mtext></mrow></msub></math></span>, it shows notable discrepancies and increased sensitivity to parameter variations at higher loadings, indicating the need for further refinements to achieve better alignment with experimental observations. This research provides essential insights into optimizing ASSB cathode designs, offering a robust framework for refining DEM models to predict and enhance battery performance under various conditions.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"535 ","pages":"Article 146536"},"PeriodicalIF":5.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermochemical measurements of FeCl2 in LiCl via electromotive force, coulometric titration, and cyclic voltammetry","authors":"Jarrod Gesualdi,&nbsp;Eva S. Schneiderlochner,&nbsp;Timothy Lichtenstein,&nbsp;Krista L. Hawthorne","doi":"10.1016/j.electacta.2025.146694","DOIUrl":"10.1016/j.electacta.2025.146694","url":null,"abstract":"<div><div>The thermochemical properties of FeCl₂ in the LiCl–FeCl₂ binary system were determined at 913 K using electromotive force (emf) cells containing pre-made and coulometrically titrated molten salt compositions. Coulometric titration to <em>in-situ</em> change the salt composition utilizes the multiple valences of Fe ions and the tendency of Fe³⁺ions to comproportionate with Fe metal, forming additional Fe²⁺. The emf results were used to define the compositions in which Henry’s law is applicable, up to approximately 2 mol % FeCl₂. Thermochemical quantities were determined from emf using a Standard Lithium Chloride Electrode (SLiCE) which defines 0 V as the reduction of Li⁺ in pure LiCl at all temperatures. Validation of emf measurements was performed by comparing the formal potential measured by using cyclic voltammetry (2.224 ± 0.013 V vs SLiCE) and emf measurements (2.236 ± 0.004 V). This work shows that coulometric titration of an electroactive species that undergoes comproportionation can be used to rapidly obtain granular emf data in molten salt systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"536 ","pages":"Article 146694"},"PeriodicalIF":5.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Charge storage of Mo/Ti based MXenes for electrochemical capacitor application","authors":"Masoud Foroutan Koudahi ,&nbsp;Adam Ślesiński ,&nbsp;Elżbieta Frąckowiak","doi":"10.1016/j.electacta.2025.146691","DOIUrl":"10.1016/j.electacta.2025.146691","url":null,"abstract":"<div><div>This study provides insight into the preparation and energy storage response of double-transition metal carbides. Controlling etching parameters allows us to prepare Mo/Ti-based carbides with different energy storage performance. Effective strategies were employed to design MXene cells with more optimized and practical electrochemical performance. High-mass loading electrodes were integrated into symmetric and asymmetric systems using aqueous electrolytes with a wide pH range. Various alternatives, including asymmetric cell assembly, redox-active electrolytes, and replacing (+) MXene electrode by carbon electrode, were tested to improve the charge storage of the positive electrode, thereby improving the full cell response. In acidic media, an asymmetric cell based on (-) MXene and (+) BP2000 carbon black showed a high cell voltage (1.3 V) and a long cyclability (8000 cycles at 1 A <em>g</em>⁻¹) compared to the symmetric cell (0.8 V). We further showed that the cell capacitance in 1 M NaI can be significantly enhanced once (+) MXene is replaced by carbon black or activated carbon.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"535 ","pages":"Article 146691"},"PeriodicalIF":5.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}