Electrochimica Acta最新文献

{"title":"Extrapolability of Machine Learning for Determining Additive Concentrations in Copper Electrolyte","authors":"Hyunwoo Jeon, Hyeonsu Kim, Jeong Wuk Kim, Young Yoon, Myung Jun Kim, Jae Jeong Kim","doi":"10.1016/j.electacta.2025.146503","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146503","url":null,"abstract":"Measurement of additive concentrations in acidic electrolytes is essential for maintaining the high reliability of the Cu electrodeposition process. Conventional cyclic voltammetric stripping (CVS) methods limit both accuracy and efficiency, often requiring excessive analytical time, and are not inherently suitable for in-situ analysis. An advanced analytical tool is needed to improve the Cu electrodeposition process, with machine learning (ML)-based techniques emerging as leading candidates due to their ability to simultaneously extract the concentrations of multiple additives from a single voltammogram. While ML-based tools ensure higher accuracy and significantly shorter analytical times, further research is necessary to advance these techniques. This study focuses on the extrapolability of ML models for determining additive concentrations. A case study involving the PEG-Cl^--SPS combination is conducted by intentionally limiting the concentration range for model training, followed by prediction of the three additives across the full concentration range. Various ML models are evaluated in terms of both upward and downward extrapolability by investigating the relationship between test and predicted concentrations of the three additives. The artificial neural network (ANN) model demonstrates the highest extrapolability in simultaneously determining the concentrations of three additives.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"11 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114321","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":"Realizing Ultra-Fast Ionic Transport in the Cost-effective Chlorospinel Cathode for All-Solid-State Lithium-Ion Batteries","authors":"Yu Wang, Tianrui Sun, Linnan Bi, Xin Long, Jie Yan, Hui Tang, Ying Lin, Sizhe Wang, Jiaxuan Liao","doi":"10.1016/j.electacta.2025.146521","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146521","url":null,"abstract":"All-solid-state batteries (ASSBs) are widely regarded as the next generation of the most potential energy storage technology due to its advantages in energy density. However, the inherently low ionic conductivity of conventional cathode materials necessitates the incorporation of ionic additives in composite cathode, leading to a low mass ratio of active materials and thereby severely restricting the energy density of ASSBs. Herein, this study reports a series of novel chlorospinel cathodes Li_2-2xFe_1+xCl₄ (x = 0-0.15) with high ionic conductivity. In this system, the phase transition from Cmmm to Fd-3m can be achieved through precise regulation of x content, with the associated ionic conduction mechanism being comprehensively elucidated. Li_1.9Fe_1.05Cl₄ enabled by optimized lithium-ion coordination environments and conduction pathways, delivers ultra-high ionic conductivity (6.15 × 10⁻⁵ S cm⁻¹ at 30°C) and remarkable rate capability (88% capacity retention after 300 cycles at 3C). Notably, exceptional cycling stability is demonstrated by the composite cathode with 95 wt% active materials content, with 580 cycles being sustained at a mass loading of 6.4 mg cm⁻² without ionic additives being required. <em>Ex situ</em> XRD is employed to reveal the structural evolution of Li_1.9Fe_1.05Cl₄ during lithium extraction/insertion processes. This research provides a crucial reference for the development of high-ionic conductivity and low-cost all-solid-state battery cathode design strategies.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"156 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114326","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":"Passivation study of AISI 316L under PWR PW conditions via Electrochemical Noise (EN)","authors":"E. Ramoutsakis ,&nbsp;C. Bataillon ,&nbsp;E. Blanchard ,&nbsp;C. Cabet ,&nbsp;C. Guerre","doi":"10.1016/j.electacta.2025.146388","DOIUrl":"10.1016/j.electacta.2025.146388","url":null,"abstract":"<div><div>Long-term current vs. time experiments (100–200 <em>hrs</em>) were performed in boric acid/lithium hydroxide buffer at 320 °C &amp; 130 bars for five anodic overpotentials, ranging from 0.1 to 0.4 <em>V</em>, to achieve the steady-state anodic current at each overpotential. The remarkable observation was that all currents were noisy, i.e., consisting of a stationary baseline and more or less intense anodic transients. This electrochemical noise was characterized using the Power Spectral Density spectra over a frequency ranging from 3 <em>Hz</em> down to 0.1 <em>m<em>Hz</em></em>. These spectra exhibited a low-frequency plateau and a high-frequency roll-off described by a <em>power-law</em> function with a single slope, except for <span><math><mi>η</mi></math></span> = 0.1 <em>V</em>. The infinite integral of the PSD spectrum quantifies the current noise level. This initial approach enables a comparison of the DC anodic current and the average anodic current noise intensity on the same scale (A). This comparison revealed that their variations with overvoltage differed significantly, suggesting that the total current consisted likely of two distinct anodic components. Based on the <em>Point Defect Model</em>, we suggest that the oxide growth phase at the expense of the metal could be a time-discontinuous process, consisting of a series of elementary anodic events characterized by exponential time decay and distributed over time. In contrast, the DC current would be associated with metal-atom oxidation, which is considered a time-continuous process.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"533 ","pages":"Article 146388"},"PeriodicalIF":5.5,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104004","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":"Ion replacement to construct coral-like montmorillonite/manganese-cobalt bimetallic oxide for high-performance supercapacitors with aqueous electrolyte","authors":"Yu-Han Yuan ,&nbsp;Gui-Fang Li ,&nbsp;Shuang-Lin Cai ,&nbsp;Jin-Wei Yan ,&nbsp;Jia Liang ,&nbsp;Hai Huang ,&nbsp;Long-Long Jin ,&nbsp;Ye Zeng ,&nbsp;Jian-Chun Weng ,&nbsp;Xiao-Hong Fan ,&nbsp;Yi Li ,&nbsp;Ding-Rong Deng ,&nbsp;Qi-Hui Wu","doi":"10.1016/j.electacta.2025.146515","DOIUrl":"10.1016/j.electacta.2025.146515","url":null,"abstract":"<div><div>With the growth demand of new energies and the limitations of traditional fossil fuels, the development of efficient and environmentally friendly energy storage technologies for the new energies have become crucial. In this study, montmorillonite (MON) was used as the substrate to prepare a novel composite electrode material with manganese-cobalt oxide (HSMnCo), which is in-situ grown on the surface of MON. The manganese-cobalt oxide grown on the surface of MON fills the voids between the MON lamellae, preventing the agglomeration of MON lamellae and keeping it in a relatively loose structure. Meanwhile, MON has a high ion exchange capacity, and the Si⁴⁺ between its layers can undergo exchange reactions with Mn²⁺ and Co²⁺. Moreover, there is a synergistic and competitive effect between Mn²⁺ and Co^2+, which changes the nucleation sites, nucleation number and growth process of manganese-cobalt oxide on the surface of MON. As a result, HSMnCo with a unique coral-like structure with multiple wrinkles and layers is obtained, significantly increasing the specific surface area (212 m²∙g^-1) and porosity of the composite electrode material. Electrochemical tests showed that HSMnCo has a specific capacitance as high as 1235 F∙g^-1 at a current density of 0.5 A∙g^-1 and still retains 91.6 % of its initial capacity after 5000 cycles, demonstrating excellent cycling stability. The synergistic effect of manganese-cobalt bimetals optimizes the electron transport path, reduces the charge transfer resistance (Rct = 3.58Ω), and improves the power density (279.83 W∙kg⁻¹) and energy density (43.53 Wh∙kg^-1). In addition, when it was applied to zinc-ion supercapacitors, the long cycle capacity retention rate is further increased to 94.7 %, and when the power density is 374.78 W∙kg^-1, the energy density reaches 177.50 Wh∙kg^-1. This study not only provides new ideas for the high value utilization of waste resources such as silicate minerals but also promotes the development of green and low cost electrode materials for supercapacitors.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"533 ","pages":"Article 146515"},"PeriodicalIF":5.5,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114328","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-efficiency anion exchange membranes based on fluorinated grafted poly (aryl piperidines): Achieving good ionic conductivity and dimensional stability","authors":"Xunwang Tang ,&nbsp;Zongxue Yu ,&nbsp;Junlei Tang ,&nbsp;Guangcheng Yang ,&nbsp;Xiuzhu Zhang ,&nbsp;Yu Chen ,&nbsp;Jiajia Hou ,&nbsp;Hongye Xu ,&nbsp;Jianjun Wu","doi":"10.1016/j.electacta.2025.146520","DOIUrl":"10.1016/j.electacta.2025.146520","url":null,"abstract":"<div><div>The development of anion-exchange membrane water electrolyzers (AEMWE) offers significant potential for sustainable hydrogen production, but the practical adoption of anion exchange membranes (AEMs) is hindered by their inherent performance limitations. To overcome this challenge, we developed a series of poly (biphenylene-co-1,2-diphenylethane) piperidine AEMs featuring grafted hydrophobic fluorinated side chains by precisely controlling the grafting rate. The fluorinated side chains not only promote microphase separation and reduce ionic conduction resistance, but also significantly enhance the dimensional stability of the AEMs. Specifically, the QPBDP-TF-40 membrane exhibits good ionic conductivity (163.6 mS cm⁻¹ at 80 °C), and with increasing grafting rate the QPBDP-TF-80 membrane exhibits low swelling rate (16 % at 80 °C). QPBDP-TF-60 shows good chemical stability with ionic conductivity retention of 78.3 % after 1000 h immersion in 2 M NaOH solution at 80 °C. In addition, the membrane electrode assembled based on QPBDP-TF-40 membranes exhibits considerable current density in AEMWE (1.36 A cm⁻² achieved at 2.1 V) and stable operation at a current density of 500 mA cm⁻² for 72 h. The above results indicate that fluoride-grafted QPBDP-TF-X exhibits a large potential for application in AEMWE.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"533 ","pages":"Article 146520"},"PeriodicalIF":5.5,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114390","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":"Application of Potential Measurements and Sweep Voltammetry Methods with Ni/NiO/MgO Reference Electrode for Measurement of Oxide Ions in Molten CaCl2-CaO-Ca0","authors":"Olivia R. Dale, Chao Zhang, Michael F. Simpson","doi":"10.1016/j.electacta.2025.146470","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146470","url":null,"abstract":"Certain pyroprocessing techniques, such as direct oxide reduction (DOR), utilize a molten CaCl₂ as the electrolyte. The DOR process is used to reduce PuO₂ to Pu metal via Ca metal. A measurement of the CaO concentration could be used to know when the reaction has gone to completion. The solubility and stability of the oxide ions in molten CaCl₂ are critical aspects of these techniques. This study investigated electrochemical methods such as open circuit potential, cyclic voltammetry, and normal pulse voltammetry using a Ni/NiO reference electrode and tungsten working and counter electrodes. These methods tracked variations in calcium oxide concentration within molten CaCl₂-Ca. Key findings indicate that the OCP decreases significantly with dissolved Ca in pure CaCl₂ but increases with CaO additions, up to 5.1 wt% CaO. Correlations between oxidation current density and CaO concentration were established, contingent on the use of clean or new W working electrodes for cyclic voltammetry and normal pulse voltammetry methods. The study also identified issues related to surface contamination affecting measurements and established the stability of the Ni/NiO/MgO reference electrode over extended immersion periods, supporting its application in electrochemical monitoring.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"33 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104005","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":"Effect of magnetic field on electrochemical properties of cobalt-based pseudosupercapacitors","authors":"Guliqire tuersun,&nbsp;Hugang Cui,&nbsp;Wenjiao Li,&nbsp;Yulong Wang,&nbsp;Yan Ma,&nbsp;Kai Feng,&nbsp;Changping Yang","doi":"10.1016/j.electacta.2025.146473","DOIUrl":"10.1016/j.electacta.2025.146473","url":null,"abstract":"<div><div>In this paper, we investigated the electrochemical behavior of cobalt ferrite based (CoFe₂O₄) and its effects on its electrical properties under magnetic field conditions. We prepared the CoFe₂O₄ pseudocapacitive anode material by hydrothermal method. The structure and morphology were characterized by XRD, SEM, XPS and VSM. The electrochemical behavior and electrical properties of CoFe₂O₄ were tested and analyzed by cyclic voltammetry (CV), constant current charge and discharge (GCD), and AC impedance (EIS) under magnetic field conditions. The results showed that the applied magnetic field significantly improved the specific capacitance, energy density, and charge transport efficiency of the CoFe₂O₄. Under 7000 Gs (0.7 T) magnetic field, the specific capacitance of CV test increases from 163.9 F/g at zero field to 243 F/g, the lift ratio is 48.3 %, and the corresponding discharge time extends from 98 s at zero field to 143 s, the lift ratio is 51 %. The analysis demonstrated that the magnetic field affects the electron transport and ion diffusion process of the electrode material. This improves the electrochemical properties of the CoFe₂O₄. This study proposes a novel strategy and provides experimental evidence for magnetic field-regulated optimization of pseudocapacitive electrode materials.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"532 ","pages":"Article 146473"},"PeriodicalIF":5.5,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144099732","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":"Fabrication of high cycling stability flexible micro-supercapacitor using electrodeposited polyaniline-nitrogen sulphur doped carbon dot binary nanocomposites","authors":"M Architha, P K Neena, Navaneeth Punnakkal, T G Satheesh Babu, Punathil Vasu Suneesh","doi":"10.1016/j.electacta.2025.146518","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146518","url":null,"abstract":"Micro-supercapacitors fabricated using polyaniline are ideal for the energy requirements in flexible and wearable electronic devices. Their drawback of low cycling stability due to swelling can be minimised using nanocomposites of polyaniline. This work aims to fabricate a micro-supercapacitor using electrodeposited polyaniline-carbon dot nanocomposite and validate its capacitive performance. Nitrogen and sulphur co-doped carbon dots synthesised via the hydrothermal method showed a high quantum efficiency of 70.02% with respect to quinine sulphate in sulfuric acid medium. Electrodeposited PANI/N-S doped carbon dot binary nanocomposite showed an areal capacitance of 990 mF cm^-2, which is much higher compared to pristine PANI with 754 mF cm^-2. Two-electrode symmetric micro-supercapacitor fabricated using PVA-H₂SO₄ gel electrolyte showed an areal capacitance of 276.9 mF cm^-2 at 0.4 mA cm^-2 with a high energy density of 24.6 µWh cm^-2 and a power density of 0.17 mW cm^-2. In addition to this, the fabricated device exhibited excellent cycling stability with 98.49% capacitance retention even after 15000 cycles. The device also showed 93.3% capacitance retention even after 2000 bending cycles. Thus, the fabricated micro-supercapacitor can contribute to flexible as well as portable electronic applications, as the need for miniaturized energy storage devices is in high demand.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"1 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114470","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":"Enhanced electrochemical performance and photocatalytic activity of mixed-phase anatase/rutile TiO2 @ SiO2 core-shell nanoparticles","authors":"S. Nirmala, M. Jose","doi":"10.1016/j.electacta.2025.146407","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146407","url":null,"abstract":"This work provides a comprehensive investigation of the electrochemical and photocatalytic activity of anatase/rutile mixed-phase TiO₂@SiO₂ core-shell nanoparticles. From X-ray diffraction analysis, the tuned weight percentage of the anatase and rutile phases for varying calcination temperatures was determined. The different chemical bonds and active energy modes of the dual phase were studied using the FTIR and Raman analysis. The mixed-phase compositions exhibited a gradual redshift in absorbance strength as observed from the UV-Visible spectroscopy. The spherical morphology, lower particle size, and the core-shell formation were confirmed using TEM analysis. The XPS analysis detected the prevalent presence of Ti⁴⁺, Si⁴⁺ elements. The highest BET surface area measurements (522 m²/g) of TiO₂@SiO₂ core-shell nanoparticles enhanced the photoactivity to achieve 95% efficiency in degrading Congo red dye. Also, the mixed-phase TiO₂@SiO₂ nanoparticles have shown a remarkable specific capacitance of 471.8 F/g^-1 at the current density of 1 A/g^-1 for 5000 cycles with 94% capacitance retention.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"77 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104007","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":"Corrosion protection of large-scale 304 stainless steel via Co-MOF coated the spaced TiO2 nanotube array photoanodes","authors":"Qianxilong Wang ,&nbsp;Jiakuo Chen ,&nbsp;Jiansheng Wang ,&nbsp;Xiongfeng Zeng ,&nbsp;Ruimin Wang ,&nbsp;Yingna Zhao","doi":"10.1016/j.electacta.2025.146514","DOIUrl":"10.1016/j.electacta.2025.146514","url":null,"abstract":"<div><div>In this paper, TiO₂ nanotube arrays with gap characteristics were designed and fabricated. Moreover, by adjusting the ratio of metal ions to ligands (1:20), a fully coated Co-MOF/TiO₂ composite photoanode was obtained; Secondly, tests such as XPS and EPR were adopted and combined with theoretical calculations to verify the construction of Type II heterojunctions, which promoted the separation of photogenerated electron-hole pairs and thereby enhanced the cathodic protection effect of the composite photoanode. Finally, to promote green and environmentally friendly anti-corrosion materials, an in-depth study was conducted on the anti-corrosion and anti-pitting effects of composite photoanodes on 304SS with different application areas (1cm²,25cm²,100cm²).</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"533 ","pages":"Article 146514"},"PeriodicalIF":5.5,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104006","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}