The interaction of calcium ions with gramicidin A (gA) ion channels represents a fundamental process with significant implications for understanding ion channel regulation in biological membranes. This study employs electrochemical impedance spectroscopy (EIS), surface-enhanced infrared absorption spectroscopy (SEIRAS), and Langmuir trough experiments to unravel the multifaceted mechanism of calcium-induced blockage of gA channels in a DOPC lipid bilayer. The findings reveal that calcium ions interact with the polar headgroups of DOPC lipids, inducing dehydration and increased packing density, which reduce the mobility of gramicidin monomers. Structural analysis highlights significant elongation of the gA helices, weakening of hydrogen bonds, and a shift in the conformational equilibrium towards inactive monomeric forms. These observations challenge the conventional view of calcium ion blockage being solely due to steric hindrance, proposing instead a broader mechanism involving alterations in both the membrane environment and peptide structure. This novel perspective on calcium-ion-induced ion channel modulation provides valuable insights for designing biomimetic systems and developing therapeutic strategies targeting ion channel dysfunction.
{"title":"Insight into the Mechanism of Calcium-Induced Blockage of Gramicidin A Ion Channels","authors":"Paria Pashazadeh Panahi, Damian Dziubak, Dorota Matyszewska, Mariusz Maciorowski, Sławomir Sęk","doi":"10.1016/j.electacta.2025.146292","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146292","url":null,"abstract":"The interaction of calcium ions with gramicidin A (gA) ion channels represents a fundamental process with significant implications for understanding ion channel regulation in biological membranes. This study employs electrochemical impedance spectroscopy (EIS), surface-enhanced infrared absorption spectroscopy (SEIRAS), and Langmuir trough experiments to unravel the multifaceted mechanism of calcium-induced blockage of gA channels in a DOPC lipid bilayer. The findings reveal that calcium ions interact with the polar headgroups of DOPC lipids, inducing dehydration and increased packing density, which reduce the mobility of gramicidin monomers. Structural analysis highlights significant elongation of the gA helices, weakening of hydrogen bonds, and a shift in the conformational equilibrium towards inactive monomeric forms. These observations challenge the conventional view of calcium ion blockage being solely due to steric hindrance, proposing instead a broader mechanism involving alterations in both the membrane environment and peptide structure. This novel perspective on calcium-ion-induced ion channel modulation provides valuable insights for designing biomimetic systems and developing therapeutic strategies targeting ion channel dysfunction.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"1 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862557","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}
Pub Date : 2025-04-23DOI: 10.1016/j.electacta.2025.146285
Monali Priyadarshini, Azhan Ahmad, Shraddha Yadav, Makarand M. Ghangrekar
The present investigation articulates the application of a MIL-53(Fe) metal-organic framework (MOF)-derived Fe3O4 and multi-walled carbon nanotubes (cFe@MWCNT) composite as cathode catalyst in bio-electro-Fenton (BEF) and bio-electro-peroxone (BEP) systems. Both the systems were comparatively inspected for the in-situ production of hydrogen peroxide (H2O2), further turning into hydroxyl radical (˙OH) to degrade the acridine orange (ACO) dye. The k value for the degradation of ACO in BEF-cFe@MWCNT was 0.0075 min−1, which was 17.3-fold lower than the k value attained by the BEP-cFe@MWCNT system (0.1298 min−1). Interestingly, the baffling in the BEP system increased the degradation rate from 0.0575 to 0.1298 min−1. Further, the ACO degradation in the secondary treated sewage was determined to be 78.51 ± 3.02% (240 min) and 83.2 ± 2.7% (50 min) in BEF-cFe@MWCNT and BEP-cFe@MWCNT, respectively. The demethylation reaction, initiated by the ˙OH attack, was identified as the primary pathway for ACO degradation in both systems. Simultaneously, the intrinsic microbial activity in the anodic chamber was capable of generating power of 120.0 ± 2.2 and 103.6 ± 4.7 mW m−2 in BEF and BEP, respectively. A comprehensive comparative assessment of both systems was conducted based on pollutant degradation, power generation, and operational cost. Overall, results indicated the superiority of the baffled BEP-cFe@MWCNT system towards emerging contaminant degradation in a shorter reaction time and affirmed its practical feasibility in wastewater treatment.
{"title":"Degradation of acridine orange using sustainable bio-electro-Fenton and bio-electro-peroxone systems with MIL-53(Fe)-derived Fe3O4 and MWCNT composite: A comparative assessment","authors":"Monali Priyadarshini, Azhan Ahmad, Shraddha Yadav, Makarand M. Ghangrekar","doi":"10.1016/j.electacta.2025.146285","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146285","url":null,"abstract":"The present investigation articulates the application of a MIL-53(Fe) metal-organic framework (MOF)-derived Fe<sub>3</sub>O<sub>4</sub> and multi-walled carbon nanotubes (<em>c</em>Fe@MWCNT) composite as cathode catalyst in bio-electro-Fenton (BEF) and bio-electro-peroxone (BEP) systems. Both the systems were comparatively inspected for the <em>in-situ</em> production of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), further turning into hydroxyl radical (<strong>˙</strong>OH) to degrade the acridine orange (ACO) dye. The <em>k</em> value for the degradation of ACO in BEF-<em>c</em>Fe@MWCNT was 0.0075 min<sup>−1</sup>, which was 17.3-fold lower than the <em>k</em> value attained by the BEP-<em>c</em>Fe@MWCNT system (0.1298 min<sup>−1</sup>). Interestingly, the baffling in the BEP system increased the degradation rate from 0.0575 to 0.1298 min<sup>−1</sup>. Further, the ACO degradation in the secondary treated sewage was determined to be 78.51 ± 3.02% (240 min) and 83.2 ± 2.7% (50 min) in BEF-<em>c</em>Fe@MWCNT and BEP-<em>c</em>Fe@MWCNT, respectively. The demethylation reaction, initiated by the <strong>˙</strong>OH attack, was identified as the primary pathway for ACO degradation in both systems. Simultaneously, the intrinsic microbial activity in the anodic chamber was capable of generating power of 120.0 ± 2.2 and 103.6 ± 4.7 mW m<sup>−2</sup> in BEF and BEP, respectively. A comprehensive comparative assessment of both systems was conducted based on pollutant degradation, power generation, and operational cost. Overall, results indicated the superiority of the baffled BEP-<em>c</em>Fe@MWCNT system towards emerging contaminant degradation in a shorter reaction time and affirmed its practical feasibility in wastewater treatment.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"7 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867205","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}
Pub Date : 2025-04-22DOI: 10.1016/j.electacta.2025.146284
Nilüfer Çakmakcı Lee, Gyosik Kim, Jo Moon, Jihoon Ahn, Hosin Lee, Hyemin Kim, Junki Bang, Jiwon Sun, Ji Young Kim, Ki Yoon Bae, Samick Son, Kyoungmin Min, Youngjin Jeong
Anode-free solid-state batteries (AFSSBs) are regarded as a next-generation battery technology due to their high gravimetric/volumetric energy densities and safety. Recent studies suggested that AFSSBs require an interlayer between the current collector and solid-state electrolyte to prevent non-uniform flux and side reactions with deposited Li. Carbon nanotubes (CNTs) are effective interlayers thanks to their high Li-ion diffusivity, good chemical stability, and great mechanical strength. Nevertheless, a detailed understanding of the influence of CNT interlayer is crucial for advancing AFSSB research. Herein, the role of the CNT film interlayer on Li deposition was explored through elemental mapping analyses at various states of charge and molecular dynamics (MD) simulations. According to the results, the nano-porous CNT interlayer promotes uniform Li distribution, which improves the battery performance. Moreover, MD simulations indicate that Li atoms attach to the CNT bundles without significant aggregation, meaning that Li moves toward the current collector. It is assumed that Li diffusion through the interlayer during cycling is likely driven by two mechanisms, which are concentration gradient and electric field. This study is anticipated to serve as a foundational reference for future research on lithium diffusion in the interlayer in all-solid-state batteries (AFSSBs).
{"title":"Role of Carbon Nanotube Film Interlayer for Li-free All-Solid-State Battery","authors":"Nilüfer Çakmakcı Lee, Gyosik Kim, Jo Moon, Jihoon Ahn, Hosin Lee, Hyemin Kim, Junki Bang, Jiwon Sun, Ji Young Kim, Ki Yoon Bae, Samick Son, Kyoungmin Min, Youngjin Jeong","doi":"10.1016/j.electacta.2025.146284","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146284","url":null,"abstract":"Anode-free solid-state batteries (AFSSBs) are regarded as a next-generation battery technology due to their high gravimetric/volumetric energy densities and safety. Recent studies suggested that AFSSBs require an interlayer between the current collector and solid-state electrolyte to prevent non-uniform flux and side reactions with deposited Li. Carbon nanotubes (CNTs) are effective interlayers thanks to their high Li-ion diffusivity, good chemical stability, and great mechanical strength. Nevertheless, a detailed understanding of the influence of CNT interlayer is crucial for advancing AFSSB research. Herein, the role of the CNT film interlayer on Li deposition was explored through elemental mapping analyses at various states of charge and molecular dynamics (MD) simulations. According to the results, the nano-porous CNT interlayer promotes uniform Li distribution, which improves the battery performance. Moreover, MD simulations indicate that Li atoms attach to the CNT bundles without significant aggregation, meaning that Li moves toward the current collector. It is assumed that Li diffusion through the interlayer during cycling is likely driven by two mechanisms, which are concentration gradient and electric field. This study is anticipated to serve as a foundational reference for future research on lithium diffusion in the interlayer in all-solid-state batteries (AFSSBs).","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"43 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858083","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}
Pub Date : 2025-04-22DOI: 10.1016/j.electacta.2025.146283
Bapi Bera, Anirban Roy, Douglas S Aaron, Matthew M. Mench
In this study, tin (Sn) nanoparticles are demonstrated to effectively catalyze the reduction of CO2 to formate in an alkaline medium. Catalytically active Sn-based nanoparticles, supported on carbon black (Sn/C) and highly conductive graphene nanosheets (Sn/GN), present a promising approach to mitigating atmospheric CO2 emissions when integrated with capture technologies. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were employed to evaluate the prepared catalysts in CO2-saturated 0.5 M KHCO3 using a three-electrode rotating disk electrode (RDE) configuration. The results revealed a significantly lower charge-transfer resistance for graphene-supported tin compared to carbon black-supported tin. The CO2 reduction to formate was further demonstrated in a full electrochemical cell setup resembling the architecture of a low-temperature polymer electrolyte fuel cell (PEFC) operating in an alkaline medium with an anion exchange membrane (AEM). Performance tests were conducted with both triple-serpentine and parallel flow field architectures, showing flow rate-dependent behavior. Additionally, an ex-situ RDE technique was utilized to detect and quantify formate production during CO2 reduction in the full-cell configuration. This work highlights the importance of catalyst support materials and flow field design in optimizing CO2 electroreduction systems.
{"title":"Electroreduction of CO2 to formate on modified graphene-supported Sn nanoparticles","authors":"Bapi Bera, Anirban Roy, Douglas S Aaron, Matthew M. Mench","doi":"10.1016/j.electacta.2025.146283","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146283","url":null,"abstract":"In this study, tin (Sn) nanoparticles are demonstrated to effectively catalyze the reduction of CO<sub>2</sub> to formate in an alkaline medium. Catalytically active Sn-based nanoparticles, supported on carbon black (Sn/C) and highly conductive graphene nanosheets (Sn/GN), present a promising approach to mitigating atmospheric CO<sub>2</sub> emissions when integrated with capture technologies. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were employed to evaluate the prepared catalysts in CO<sub>2</sub>-saturated 0.5 M KHCO<sub>3</sub> using a three-electrode rotating disk electrode (RDE) configuration. The results revealed a significantly lower charge-transfer resistance for graphene-supported tin compared to carbon black-supported tin. The CO<sub>2</sub> reduction to formate was further demonstrated in a full electrochemical cell setup resembling the architecture of a low-temperature polymer electrolyte fuel cell (PEFC) operating in an alkaline medium with an anion exchange membrane (AEM). Performance tests were conducted with both triple-serpentine and parallel flow field architectures, showing flow rate-dependent behavior. Additionally, an ex-situ RDE technique was utilized to detect and quantify formate production during CO<sub>2</sub> reduction in the full-cell configuration. This work highlights the importance of catalyst support materials and flow field design in optimizing CO<sub>2</sub> electroreduction systems.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"17 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862139","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}
Pub Date : 2025-04-22DOI: 10.1016/j.electacta.2025.146286
Mohammad Furquan, Zahid Manzoor Bhat, Mohammad Qamar
Electrolyte formulation significantly impacts the electrochemical performance of redox flow batteries (RFBs) in an alkaline medium. We demonstrate that the voltage, reversibility, and galvanostatic cyclic stability of RFBs improve with a potassium hydroxide (KOH) concentration beyond 1 M (pH 14). The study shows that a high KOH concentration is more critical for catholyte-potassium ferrocyanide (PF) than anolyte-Alizarin to maintain high capacity retention in full-cell, confirmed via symmetric (x M KOH-Alizarin || x M KOH-PF) and asymmetric (x M KOH-Alizarin || y M KOH-PF) KOH concentrations. Asymmetric high KOH concentration (4 M KOH-Alizarin || 3 M KOH-PF) compared to conventional symmetric (1 M KOH-Alizarin || 1 M KOH-PF) exhibits higher discharge capacity retention (∼32%) after 200 cycles at 100% state of charge (SOC) with ∼5% higher energy efficiency at 30°C. Furthermore, our cyclic voltammetry experiments reveal that the separation (ΔE) between cathodic and anodic peaks decreases significantly with high KOH concentration at the graphite felt compared to the glassy carbon electrode, enhancing the redox couple's reversibility, therefore emphasizing its crucial role in the RFBs.
{"title":"Electrolyte engineering beyond the conventional alkaline concentration for high-capacity retention of aqueous redox flow batteries","authors":"Mohammad Furquan, Zahid Manzoor Bhat, Mohammad Qamar","doi":"10.1016/j.electacta.2025.146286","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146286","url":null,"abstract":"Electrolyte formulation significantly impacts the electrochemical performance of redox flow batteries (RFBs) in an alkaline medium. We demonstrate that the voltage, reversibility, and galvanostatic cyclic stability of RFBs improve with a potassium hydroxide (KOH) concentration beyond 1 M (pH 14). The study shows that a high KOH concentration is more critical for catholyte-potassium ferrocyanide (PF) than anolyte-Alizarin to maintain high capacity retention in full-cell, confirmed via symmetric (x M KOH-Alizarin || x M KOH-PF) and asymmetric (x M KOH-Alizarin || y M KOH-PF) KOH concentrations. Asymmetric high KOH concentration (4 M KOH-Alizarin || 3 M KOH-PF) compared to conventional symmetric (1 M KOH-Alizarin || 1 M KOH-PF) exhibits higher discharge capacity retention (∼32%) after 200 cycles at 100% state of charge (SOC) with ∼5% higher energy efficiency at 30°C. Furthermore, our cyclic voltammetry experiments reveal that the separation (ΔE) between cathodic and anodic peaks decreases significantly with high KOH concentration at the graphite felt compared to the glassy carbon electrode, enhancing the redox couple's reversibility, therefore emphasizing its crucial role in the RFBs.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"41 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858084","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}
Pub Date : 2025-04-22DOI: 10.1016/j.electacta.2025.146282
Xiaodong He, Xingjin Xiao, Yongxiang Guan, Xinshuang Cui
Understanding ion transport behaviors in confined ionic liquid (IL)/aqueous solution systems is crucial for advancing nanofluidic device applications. In this study, we investigate the ionic current behaviors of such systems using quartz nanopipettes, revealing significant ionic current rectification (ICR) phenomena at the nanoscale, which are absent at the microscale. Experimental results show that in the absence of an external bias voltage, diffusion currents in nanopipettes are negative due to the liquid-junction potential at the IL/aqueous interface. The rectification ratio (R) increases from 1.47 to 11.64 as the KCl electrolyte concentration increases from 0.01 M to 1 M, indicating a unique behavior distinct from conventional aqueous systems. Additionally, different ILs exhibit varying rectification strengths, following the sequence: [Bmim][BF4] > [Bmim][NTf2] > [Bmim][PF6] > [Bmim][N(CN)2]. To further elucidate the underlying mechanisms, we conducted finite element simulation using a Poisson-Nernst-Planck model. The simulation results further demonstrate that IL diffusion, electrostatic interactions, and electric double layer effects collectively influence the observed ICR behavior. These findings provide new insights into ion transport in IL/aqueous systems and offer valuable guidelines for designing nanopipette-based ion sensors and nanofluidic devices.
{"title":"Ionic current rectification behaviors in quartz nanopipettes with ionic liquids/aqueous solution systems","authors":"Xiaodong He, Xingjin Xiao, Yongxiang Guan, Xinshuang Cui","doi":"10.1016/j.electacta.2025.146282","DOIUrl":"10.1016/j.electacta.2025.146282","url":null,"abstract":"<div><div>Understanding ion transport behaviors in confined ionic liquid (IL)/aqueous solution systems is crucial for advancing nanofluidic device applications. In this study, we investigate the ionic current behaviors of such systems using quartz nanopipettes, revealing significant ionic current rectification (ICR) phenomena at the nanoscale, which are absent at the microscale. Experimental results show that in the absence of an external bias voltage, diffusion currents in nanopipettes are negative due to the liquid-junction potential at the IL/aqueous interface. The rectification ratio (R) increases from 1.47 to 11.64 as the KCl electrolyte concentration increases from 0.01 M to 1 M, indicating a unique behavior distinct from conventional aqueous systems. Additionally, different ILs exhibit varying rectification strengths, following the sequence: [Bmim][BF<sub>4</sub>] > [Bmim][NTf<sub>2</sub>] > [Bmim][PF<sub>6</sub>] > [Bmim][N(CN)<sub>2</sub>]. To further elucidate the underlying mechanisms, we conducted finite element simulation using a Poisson-Nernst-Planck model. The simulation results further demonstrate that IL diffusion, electrostatic interactions, and electric double layer effects collectively influence the observed ICR behavior. These findings provide new insights into ion transport in IL/aqueous systems and offer valuable guidelines for designing nanopipette-based ion sensors and nanofluidic devices.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"528 ","pages":"Article 146282"},"PeriodicalIF":5.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858081","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}
Pub Date : 2025-04-21DOI: 10.1016/j.electacta.2025.146279
Shuling Liu , Yanling Hu , Xinyi Lu , Bowen Xin , Zeyi Wang , Yihao Li , Zhikai Hu , Chao Wang
Electrodeposited nickel, cobalt, and their alloys are critical for applications including energy storage, electrocatalysis and magnetic devices. Traditional aqueous electrodeposition suffers from hydrogen evolution, causing embrittlement, while deep eutectic solvents (DES) offer a promising alternative owing to their low water activity. Here, amino acid-metal nitrate DES (Ni(NO3)2 and/or Co(NO3)2-L‑serine) are introduced, and the electrochemical nucleation and growth mechanisms of Ni, Co, and their alloys are investigated. Cyclic voltammetry and potentiostatic transient analyses reveal potential-dependent nucleation and growth behavior. Electrodeposition of Ni from Ni(NO3)2/L‑serine DES exhibits a two-stage nucleation and growth behavior. The electrodeposition of Co from Co(NO3)2/L‑serine DES follows a three-dimensional progressive nucleation mechanism. New models integrating proton reduction and adsorption with Scharifker-Mostany model for monometallic deposition and with Scharifker model for alloy deposition are proposed to interpret potentiostatic current transient behavior. The deposits are characterized by X-ray diffraction and scanning electron microscopy and the crystalline metal phases are confirmed.
{"title":"Electrochemical metal nucleation and growth mechanism from metal nitrate-L-serine deep eutectic solvent","authors":"Shuling Liu , Yanling Hu , Xinyi Lu , Bowen Xin , Zeyi Wang , Yihao Li , Zhikai Hu , Chao Wang","doi":"10.1016/j.electacta.2025.146279","DOIUrl":"10.1016/j.electacta.2025.146279","url":null,"abstract":"<div><div>Electrodeposited nickel, cobalt, and their alloys are critical for applications including energy storage, electrocatalysis and magnetic devices. Traditional aqueous electrodeposition suffers from hydrogen evolution, causing embrittlement, while deep eutectic solvents (DES) offer a promising alternative owing to their low water activity. Here, amino acid-metal nitrate DES (Ni(NO<sub>3</sub>)<sub>2</sub> and/or Co(NO<sub>3</sub>)<sub>2</sub>-L‑serine) are introduced, and the electrochemical nucleation and growth mechanisms of Ni, Co, and their alloys are investigated. Cyclic voltammetry and potentiostatic transient analyses reveal potential-dependent nucleation and growth behavior. Electrodeposition of Ni from Ni(NO<sub>3</sub>)<sub>2</sub>/L‑serine DES exhibits a two-stage nucleation and growth behavior. The electrodeposition of Co from Co(NO<sub>3</sub>)<sub>2</sub>/L‑serine DES follows a three-dimensional progressive nucleation mechanism. New models integrating proton reduction and adsorption with Scharifker-Mostany model for monometallic deposition and with Scharifker model for alloy deposition are proposed to interpret potentiostatic current transient behavior. The deposits are characterized by X-ray diffraction and scanning electron microscopy and the crystalline metal phases are confirmed.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"528 ","pages":"Article 146279"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853239","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}
Pub Date : 2025-04-21DOI: 10.1016/j.electacta.2025.146281
Junwei Shan, Zhiqing Zhu, Zhihao Chen, Feng Du, Quan Li
Silicon (Si)-based anode materials are promising for lithium-ion batteries (LIBs) due to their high theoretical capacity, but challenges such as large volume changes during cycling and low conductivity hinder their practical application. In this study, we report a self-supporting, binder-free Si/C composite anode featuring structurally continuous, three-dimensional (3D) graphene-like silicon thin films, encapsulated by a 3D carbon film framework and coated with an amorphous carbon layer. This architecture is specifically designed to mitigate the volume expansion of silicon during cycling and enhance electrical conductivity. The spacing between the carbon films is systematically controlled by applying varying pressure compressions, allowing us to evaluate its effect on limiting the volume expansion of Si. At a current density of 1 A g−1, the C@Si@CPGN-3MPa anode exhibits an initial coulombic efficiency (ICE) of 84.08 %, a stable specific capacity of 825.3 mAh g−1, and excellent long-term cycling stability. This work provides valuable insights into the design of self-supporting Si-based anodes that offer long cycle life, high energy density, and enhanced structural stability, which are crucial for advancing the practical application of Si in LIBs.
{"title":"Si/C Composites Based on Bubble 3D Graphene-like Porous Materials as Self-supporting Anodes for High-Performance Lithium-Ion Batteries","authors":"Junwei Shan, Zhiqing Zhu, Zhihao Chen, Feng Du, Quan Li","doi":"10.1016/j.electacta.2025.146281","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.146281","url":null,"abstract":"Silicon (Si)-based anode materials are promising for lithium-ion batteries (LIBs) due to their high theoretical capacity, but challenges such as large volume changes during cycling and low conductivity hinder their practical application. In this study, we report a self-supporting, binder-free Si/C composite anode featuring structurally continuous, three-dimensional (3D) graphene-like silicon thin films, encapsulated by a 3D carbon film framework and coated with an amorphous carbon layer. This architecture is specifically designed to mitigate the volume expansion of silicon during cycling and enhance electrical conductivity. The spacing between the carbon films is systematically controlled by applying varying pressure compressions, allowing us to evaluate its effect on limiting the volume expansion of Si. At a current density of 1 A g<sup>−1</sup>, the C@Si@CPGN-3MPa anode exhibits an initial coulombic efficiency (ICE) of 84.08 %, a stable specific capacity of 825.3 mAh g<sup>−1</sup>, and excellent long-term cycling stability. This work provides valuable insights into the design of self-supporting Si-based anodes that offer long cycle life, high energy density, and enhanced structural stability, which are crucial for advancing the practical application of Si in LIBs.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"10 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853240","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}
Pub Date : 2025-04-21DOI: 10.1016/j.electacta.2025.146278
Bao Qin , Jing Hu , Zhong Wu , Xiuping Yang , Zhigao Xue , Qiang Chen , Jianli Zhang , Guangya Hou , Bozhen Wu , Yiping Tang , Wenbin Hu
Developing new pulsed electrodeposition process for preparing high-strength electroplated copper foil as anode current collector for lithium-ion batteries is a highly promising research direction. This study reveals that appropriate pulsed electrodeposition process parameters, such as electrolyte temperature, current density, duty cycle and additives, can significantly enhance the tensile strength and elongation of copper foil. Under the same conditions, the mechanical properties of copper foil prepared by adding bis-(3-sulfonpropyl)-disulfide (SPS) are the most significant improvement, the tensile strength of electroplated copper foil reaches 640 MPa, while it is only 450 MPa by direct current electrodeposition. The main reason for the improvement in mechanical properties is the significant increase in the number of twins and dislocations under the combined effect of pulsed deposition and SPS, as well as the noticeable reduction in the thickness of twin lamellae and grain size.
{"title":"Effect of pulse electrodeposition process on the microstructure and properties of electrolytic copper foil as anode current collectors","authors":"Bao Qin , Jing Hu , Zhong Wu , Xiuping Yang , Zhigao Xue , Qiang Chen , Jianli Zhang , Guangya Hou , Bozhen Wu , Yiping Tang , Wenbin Hu","doi":"10.1016/j.electacta.2025.146278","DOIUrl":"10.1016/j.electacta.2025.146278","url":null,"abstract":"<div><div>Developing new pulsed electrodeposition process for preparing high-strength electroplated copper foil as anode current collector for lithium-ion batteries is a highly promising research direction. This study reveals that appropriate pulsed electrodeposition process parameters, such as electrolyte temperature, current density, duty cycle and additives, can significantly enhance the tensile strength and elongation of copper foil. Under the same conditions, the mechanical properties of copper foil prepared by adding bis-(3-sulfonpropyl)-disulfide (SPS) are the most significant improvement, the tensile strength of electroplated copper foil reaches 640 MPa, while it is only 450 MPa by direct current electrodeposition. The main reason for the improvement in mechanical properties is the significant increase in the number of twins and dislocations under the combined effect of pulsed deposition and SPS, as well as the noticeable reduction in the thickness of twin lamellae and grain size.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"528 ","pages":"Article 146278"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858082","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}
Pub Date : 2025-04-21DOI: 10.1016/j.electacta.2025.146280
Kaihui Dong , Yingwei Song , En-Hou Han
Two lightweight metals of Ti and Al alloys are widely applied in the aerospace industry, which are inevitably connected as Ti-Al joints in practical applications. The assembly method significantly influences the galvanic corrosion behavior of Ti-Al joints. The galvanic corrosion rate and “effect distance” of TC18 Ti alloy and 20,250 Al alloy joints assembled with the bolts of 304 stainless steel and H62 brass were investigated by electrochemical tests, finite element modelling (FEM), and neutral salt spray validation. The results indicate that the corrosion rate of the anode 2050 Al alloy increases by approximately 50 % when H62 brass bolts are employed compared to 304 stainless steel bolts. This phenomenon is attributed to the improvement of passivation film on the cathode 304 stainless steel during the galvanic corrosion process, which inhibits the charge transfer to reduce the acceleration effect. Due to the effect of solution resistance, the “effect distance” of galvanic corrosion is only approximately 5 mm. The corrosion of 2050 Al alloy around the bolts is mainly accelerated by the bolts instead of TC18, whereas other contact regions within the “effect distance” range, the TC18 Ti alloy plays a main role, and the acceleration effect is mainly determined by the cathode/anode area ratios of Ti and Al.
{"title":"Study on the galvanic corrosion of Ti-Al joints with different bolting assembly methods","authors":"Kaihui Dong , Yingwei Song , En-Hou Han","doi":"10.1016/j.electacta.2025.146280","DOIUrl":"10.1016/j.electacta.2025.146280","url":null,"abstract":"<div><div>Two lightweight metals of Ti and Al alloys are widely applied in the aerospace industry, which are inevitably connected as Ti-Al joints in practical applications. The assembly method significantly influences the galvanic corrosion behavior of Ti-Al joints. The galvanic corrosion rate and “effect distance” of TC18 Ti alloy and 20,250 Al alloy joints assembled with the bolts of 304 stainless steel and H62 brass were investigated by electrochemical tests, finite element modelling (FEM), and neutral salt spray validation. The results indicate that the corrosion rate of the anode 2050 Al alloy increases by approximately 50 % when H62 brass bolts are employed compared to 304 stainless steel bolts. This phenomenon is attributed to the improvement of passivation film on the cathode 304 stainless steel during the galvanic corrosion process, which inhibits the charge transfer to reduce the acceleration effect. Due to the effect of solution resistance, the “effect distance” of galvanic corrosion is only approximately 5 mm. The corrosion of 2050 Al alloy around the bolts is mainly accelerated by the bolts instead of TC18, whereas other contact regions within the “effect distance” range, the TC18 Ti alloy plays a main role, and the acceleration effect is mainly determined by the cathode/anode area ratios of Ti and Al.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"528 ","pages":"Article 146280"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853241","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}
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