Electrochimica Acta最新文献_第6页

The effect of competition between solvation and cathode surface adsorption on the kinetics of lithium−oxygen batteries: A model study based on nanoarray electrodes

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-14 DOI: 10.1016/j.electacta.2025.146244

Yuying Gao , Zelin Zhao , Mingjun Zhu , Ming Li , Xiaorong Zhou , Junsheng Li , Jinping Liu , Liang Xiao

The donor number (DN) of electrolyte solvents was reported to be the key factor determining LiO₂ intermediate solvation and lithium−oxygen battery (LOB) kinetics. In low-DN solvents, LiO₂ tends to adsorb onto cathode surfaces and undergoes surface-mediated reduction to Li₂O₂, while in high-DN solvents, LiO₂ is preferentially solvated and subsequently disproportionates to Li₂O₂. However, prior studies overlooked a critical issue: whether cathode surfaces can provide sufficiently strong adsorption for LiO₂, particularly in low-DN solvents. Herein, this study proposes MnO₂, NiO, and Co₃O₄ nanoarray models alongside carbon nanotubes to simultaneously investigate LiO₂ adsorption on different cathodes and solvent DN effects under consistent cathode architectures. Experimental and theoretical analyses reveal that the discharge of oxygen cathodes involves a competition between the solvation of LiO₂ intermediates and their adsorption on cathodes. When an oxygen cathode has strong adsorption of LiO₂, the adsorption and solvation compete with each other, leading to a solution mechanism in high-DN solvents and a surface mechanism in low-DN solvents. Conversely, if an oxygen cathode shows weak adsorption of LiO₂, a solution mechanism predominately occurs, regardless of whether in high- or low-DN solvents. Thus, when evaluating solvent effects on LOB kinetics, the adsorption capacity of cathode materials must be fully considered.

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引用次数: 0

Simple and cost-effective method for engineering tunable defects and functional groups for high-performance coal-derived hard carbon anodes in sodium-ion batteries

IF 6.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-14 DOI: 10.1016/j.electacta.2025.146236

Xiaohu Wang, Jie Ren, Yi Zhu, Gai Lan, Yaxin Huang, Jianfang Wang, Jun Liu, Junhui Dong, Chunguang Wei, Na Huang, Ding Nan

The development of advanced anode materials for sodium-ion batteries (SIBs) is critical for enhancing energy storage capabilities. Herein, we present a simple and cost-effective one-step carbonization method to engineer tunable defects and functional groups in coal-derived hard carbon (HC) anodes. By exploiting the inherent features of coal, such as its aromatic structure and reactive functionalities, we systematically tailor the HC microstructure through controlled carbonization. The resulting materials exhibit adjustable features, including graphite-like microcrystals, amorphous carbon domains, nanoporous networks, and oxygen-containing functional groups, enabling optimized sodium-ion storage performance. Notably, the lignite-derived HC material (L-1300) synthesized at 1300°C achieves a reversible capacity of 295 mAh g⁻¹, an initial Coulombic efficiency of 89%, and exceptional capacity retention (97%) after 500 cycles at 1 C. The enhanced electrochemical performance is attributed to the synergistic effects of engineered defects and functional groups, which facilitate efficient sodium ion transport and storage. This study demonstrates the potential of coal as a sustainable and low-cost precursor for high-performance HC anodes, offering a promising approach for next-generation SIBs.

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引用次数: 0

Machine learning assisted classification and interpretation of EIS data with experimental demonstration for chemical conversion coatings on Mg alloys

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-14 DOI: 10.1016/j.electacta.2025.146231

Debasis Saran , Neelam Mishra , Sivaiah Bathula , Kisor Kumar Sahu

Magnesium and its alloys, promising for structural applications, have significant corrosion concerns. Chemical conversion coating (CCC) is a cost-effective, scalable, and environment-friendly method to address this issue. EIS is a powerful technique frequently used in various applications, including CCCs, to model diverse electrode-electrolyte interface processes through equivalent circuits (EC). The traditional EC approach is tedious, requires human experience and imparts subjectivity. Machine Learning (ML) strategies automate the process of EC classification, identify complex patterns, reduce subjectivity and analysis time. This study focuses on the ML classification of ECs in CCCs, covering almost all realistic coating conditions and processes. We have used both linear (PCA: Principal Component Analysis and LDA: Linear Discriminant Analysis for interpretation and dimensional reductions; Logistic Regression for classification) and non-linear ML models (Naïve Bayes, Random Forest, XG Boost, Gradient Boost and 1D-CNN: all for seven-class EC classification). We observed that PCA reduced 213-dimensional feature space to 8 PCs, retaining 99% variance, whereas ∼89% of the top 10 features in LDA belong to low-frequency regions. The performance of ML models was evaluated by diverse metrics: confusion matrix, F1-score, precision, recall, Shapley Additive Explanations (SHAP), and Area under Receiver Operating Characteristic Curve (AUC). Overall, 1D-CNN model performed the best with an accuracy ∼86%, mean AUC ∼0.98, and top-2 accuracy ∼96%. From SHAP analysis, we found low-frequency phase measurements are critical for the 1D-CNN model's decision-making, signifying the importance of slow electrochemical processes. Finally, we validated best ML model with experimental data and found 1D-CNN classifier has an average R²∼0.96.

镁及其合金在结构应用方面前景广阔，但存在严重的腐蚀问题。化学转化涂层（CCC）是解决这一问题的一种具有成本效益、可扩展且环保的方法。EIS 是一种功能强大的技术，常用于包括 CCC 在内的各种应用中，通过等效电路 (EC) 模拟各种电极-电解质界面过程。传统的等效电路（EC）方法非常繁琐，需要人的经验和主观性。机器学习（ML）策略可使等效电路分类过程自动化，识别复杂模式，减少主观性和分析时间。本研究的重点是对 CCC 中的导电率进行 ML 分类，几乎涵盖了所有现实的涂层条件和工艺。我们使用了线性（PCA：主成分分析法和 LDA：线性判别分析法）方法进行解释：线性判别分析用于解释和降维；逻辑回归用于分类）和非线性 ML 模型（Naïve Bayes、Random Forest、XG Boost、Gradient Boost 和 1D-CNN：均用于七级 EC 分类）。我们观察到，PCA 将 213 维特征空间缩减为 8 个 PC，保留了 99% 的方差，而 LDA 中前 10 个特征中有 89% 属于低频区域。混淆矩阵、F1-分数、精确度、召回率、Shapley Additive Explanations (SHAP) 和 Receiver Operating Characteristic Curve (AUC) 等不同指标对 ML 模型的性能进行了评估。总体而言，1D-CNN 模型表现最佳，准确率为 86%，平均 AUC 为 0.98，前 2 名的准确率为 96%。通过 SHAP 分析，我们发现低频相位测量对 1D-CNN 模型的决策至关重要，这表明缓慢电化学过程的重要性。最后，我们用实验数据验证了最佳 ML 模型，发现 1D-CNN 分类器的平均 R2 ∼ 0.96。

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引用次数: 0

Electrochemical Reduction Mechanism of 4-Nitrobenzyl Bromide in Ionogel Membranes

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-14 DOI: 10.1016/j.electacta.2025.146232

Tehreema Naeem, Silvia Mena, Jordi Hernando, Gonzalo Guirado

Ionic liquid-based electrolytes (ILs) have gained tremendous attention as sustainable, green electrolytes for electrochemical processes due to their negligible vapour pressure and high boiling points. A rising trend is to fabricate solid electrolytes based on ionic liquids to address the risk of leakage associated to liquid electrolytes. These solid electrolytes, which are commonly known as ionogel membranes (IGs), contain the intrinsic properties of ILs, while having excellent mechanical strength. These characteristics make them ideal for investigating reaction mechanisms and facilitating electrosynthesis processes. By providing a stable and conductive environment, ionogels enable precise control and monitoring of electrochemical reactions in solid electrolytes, leading to more accurate and reproducible results. Their application not only enhances our understanding of fundamental electrochemical processes but also paves the way for innovative advancements in electrosynthesis, contributing significantly to the development of new materials and technologies. In this body of research, the reduction mechanism of p-nitrobenzyl bromide (p-NBBr) is studied and disclosed in IG membranes for a first time. We successfully performed a controlled potential electrolysis of p-NBBr in IG membranes, as well as studying two different electrochemical setups to obtain the most optimal configuration. We also demonstrate that the addition of electrolyte additives, such as lithium bis(trifluorometahnesulfonyl)imide (Li TFSI), in the IG composition raises the ionic conductivity of the resulting membrane from 0.15 up to 0.2 mS/cm.

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引用次数: 0

A Pd–Pt-based bulk nanoporous alloy with continuous solubility for hydrogen

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-13 DOI: 10.1016/j.electacta.2025.146106

Sambit Bapari , Jörg Weissmüller

Metal hydrides that enable reversible solute exchange with a reservoir often exhibit a miscibility gap at room temperature. Misfit strain during two-phase coexistence may then lead to degradation on repeated charging/discharging cycles. Furthermore, the miscibility gap impairs continuous and uniform composition tuning for functional applications. We explore electrochemical dealloying as a pathway to macroscopic monolithic samples of nanoporous Pd–Pt with continuous solubility for H at room temperature. The ligament size is tunable in the range of 4–40 nm, and sorption isotherms suggest a miscibility-gap critical point marginally below room temperature. With a maximum hydrogen fraction of 0.5, we demonstrate a reversible actuation strain of 3.3 % and a high cycle stability.

引用次数: 0

One-pot exfoliation with simultaneous functionalization of graphene via wireless polarization

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-13 DOI: 10.1016/j.electacta.2025.146230

Anastasiia Bazylevska , Zviadi Zarkua , Giel Arnauts , Lino da Costa Pereira , Rob Ameloot , Miriam C. Rodríguez González , Steven De Feyter

The field of 2D materials has rapidly grown and has expanded further by the tunability of their unique properties for device fabrication. Covalent functionalization, such as spontaneous grafting and electrografting, has been employed to enhance dispersibility and optimize performance for various applications; however, several challenges still remain. Current methods often require reactive conditions that hinder control over modification uniformity or rely on conductive materials, limiting scalability. This work introduces a one-pot protocol for exfoliating and functionalizing 2D materials using wireless polarization, demonstrated with graphene. The method is conducted in water without using surfactants or toxic solvents and produces high-quality exfoliated graphene flakes, confirmed via transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Functionalization with diazonium chemistry is validated through XPS and thermogravimetric analysis combined with mass spectrometry, showcasing successful grafting. The scalable, versatile wireless approach has the potential to be applicable to a wide range of 2D materials and organic functionalization methods, offering the prospect for industrial integration and broadening possibilities in device applications.

二维材料领域发展迅猛，其独特性能的可调性进一步拓展了设备制造领域。共价官能化，如自发接枝和电接枝，已被用于提高分散性和优化各种应用的性能；然而，仍然存在一些挑战。目前的方法通常需要反应条件，这阻碍了对修饰均匀性的控制，或者依赖于导电材料，限制了可扩展性。本研究以石墨烯为例，介绍了一种利用无线极化对二维材料进行剥离和功能化的单锅协议。通过透射电子显微镜、原子力显微镜、X 射线光电子能谱（XPS）和拉曼光谱证实，该方法可在水中进行，无需使用表面活性剂或有毒溶剂，并能产生高质量的剥离石墨烯薄片。通过 XPS 和热重分析结合质谱法验证了重氮化学的功能化，展示了成功的接枝。这种可扩展的多功能无线方法有可能适用于各种二维材料和有机功能化方法，为工业集成提供了前景，并拓宽了设备应用的可能性。

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引用次数: 0

Zinc metal free polymer-based anode materials for ultralong aqueous zinc-ion rechargeable battery

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-12 DOI: 10.1016/j.electacta.2025.146211

Gouri Sankar Das , Komal Kumari , Phulladweepa Patra , Prabakaran Swaminathan , Somnath Ghosh

Aqueous Zn-ion batteries (AZIBs) have garnered significant attention for grid-level energy storage systems owing to their high safety, cost-effectiveness and environmental friendliness. However, the practical application of the AZIBs always suffers from uncontrollable Zn dendrite growth, low coulombic efficiency and the irreversible kinetics of electrodes. Herein, we propose a highly zincophilic organic polyimide-decorated graphene (PI/G) anode synthesized through straightforward polycondensation reactions featuring an optimized electronic structure with a π-conjugated network. The well-organized, high-density diimide groups in PI/G material offer more accessible electrochemically active sites and reduce the energy barrier for ion diffusion as supported by electrochemical, ex-situ characterizations and density functional theory (DFT) simulations. The synthesized PI/G anode provides a low redox potential, high specific capacity and fast rate capability. When a full AZIB is fabricated by the pairing of polymer anode with ZnMn₂O₄ cathode, the resulting dendrite-free device provides a remarkable specific capacity and ultra-long cycle stability, retaining 84 % of its capacity at 10 A g⁻¹ even after 50,000 cycles. This stability is achieved through a reversible Zn²⁺ co-participative phase transfer mechanism at redox-active sites. This study hopes to pave the way for an alternative design and development strategy for practical AZIB applications in large-scale grid energy storage systems.

{"title":"Zinc metal free polymer-based anode materials for ultralong aqueous zinc-ion rechargeable battery","authors":"Gouri Sankar Das , Komal Kumari , Phulladweepa Patra , Prabakaran Swaminathan , Somnath Ghosh","doi":"10.1016/j.electacta.2025.146211","DOIUrl":"10.1016/j.electacta.2025.146211","url":null,"abstract":"<div><div>Aqueous Zn-ion batteries (AZIBs) have garnered significant attention for grid-level energy storage systems owing to their high safety, cost-effectiveness and environmental friendliness. However, the practical application of the AZIBs always suffers from uncontrollable Zn dendrite growth, low coulombic efficiency and the irreversible kinetics of electrodes. Herein, we propose a highly zincophilic organic polyimide-decorated graphene (PI/G) anode synthesized through straightforward polycondensation reactions featuring an optimized electronic structure with a π-conjugated network. The well-organized, high-density diimide groups in PI/G material offer more accessible electrochemically active sites and reduce the energy barrier for ion diffusion as supported by electrochemical, <em>ex-situ</em> characterizations and density functional theory (DFT) simulations. The synthesized PI/G anode provides a low redox potential, high specific capacity and fast rate capability. When a full AZIB is fabricated by the pairing of polymer anode with ZnMn<sub>2</sub>O<sub>4</sub> cathode, the resulting dendrite-free device provides a remarkable specific capacity and ultra-long cycle stability, retaining 84 % of its capacity at 10 A g<sup>−1</sup> even after 50,000 cycles. This stability is achieved through a reversible Zn<sup>2+</sup> co-participative phase transfer mechanism at redox-active sites. This study hopes to pave the way for an alternative design and development strategy for practical AZIB applications in large-scale grid energy storage systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"527 ","pages":"Article 146211"},"PeriodicalIF":5.5,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823086","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}

引用次数: 0

Simplified synthesis of N, S co-doped ordered mesoporous carbon cathode via a one-step impregnation technique for superior Zn-ion hybrid supercapacitors

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-12 DOI: 10.1016/j.electacta.2025.146228

Shenghai Zhou, Na Liang, You Zhang, Xiangxiu Liu, Dongxu Ge, Hongbo Xu

Aqueous zinc-ion hybrid supercapacitors (ZHSCs) are emerging as promising energy storage devices due to their safety and low cost. The development of cathode materials with superior performance has become a focal point in ZHSC research. Herein, N, S co-doped ordered mesoporous carbons (N, S-OMC) were synthesized via a one-step impregnation of pyrrole and 2-thiophenemethanol into the mesopores of silica templates. The effect of the pyrrole-to-2-thiophenemethanol feed ratio on the microstructure and electrochemical performance of N, S-OMC was examined. The optimal electrochemical performance of N, S-OMC-25 can be attributed to the synergistic effects of well-controlled N and S doping levels, high content of pyridine N, numerous defect sites, good conductivity, ordered mesoporous channels, and a large surface area, all of which provide numerous accessible active sites for charge storage and enhanced electrochemical kinetics in ZHSCs. The N, S-OMC-25-based ZHSCs device demonstrated a high specific capacity (269 ± 1 F/g), high energy density (82 Wh/kg), and outstanding cyclic stability, retaining 95 % capacity after 10,000 cycles in 1 M ZnSO₄ and 95 % after 60,000 cycles in 3 M Zn(CF₃SO₃)₂. This work simplifies the preparation of N, S-OMC via the template method and introduces N, S-OMC carbon materials for use in aqueous ZHSCs devices.

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引用次数: 0

Mesoporous carbon materials doped with Co, Fe and nitrogen as oxygen reduction reaction electrocatalysts for anion-exchange membrane fuel cell

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-11 DOI: 10.1016/j.electacta.2025.146226

Johanna Katariina Piir , Jaana Lilloja , Maike Käärik , Jekaterina Kozlova , Arvo Kikas , Alexey Treshchalov , Jaan Aruväli , Vambola Kisand , Jaan Leis , Kaupo Kukli , Kaido Tammeveski

Mesoporous carbons (MCs) are prepared using dual-templating and doped with cobalt, iron and nitrogen for electrocatalytic applications and are characterised using various physico-chemical methods. Prepared materials are employed as oxygen reduction reaction (ORR) electrocatalysts and cathode catalysts of an anion-exchange membrane fuel cell (AEMFC). The MC materials are prepared using two novel and sustainable phenolic resin synthesis routes, while employing an easily removable soft template and MgO as a hard template to obtain feasible mesoporous texture. The content of MgO is varied in dual-templating to assess its influence on the porous structure and electrocatalytic properties. Doping is done via high-temperature pyrolysis using cobalt and iron acetate as transition metal sources and 1,10-phenanthroline as a nitrogen source. The physico-chemical characterisation shows that the preparation of MC materials and their subsequent doping has been successful. The initial assessment employing the rotating disc electrode method indicates that the synthesised catalyst materials exhibit very high electrocatalytic activity towards the ORR in alkaline media and good stability by applying 10,000 potential cycles. In AEMFC testing, the most promising cathode catalyst reveals excellent fuel cell performance by obtaining a peak power density above 500 mW cm^–2, almost the same performance as with commercial mesoporous Fe-N-C catalyst. Thus, the novel dual-templating approach taken herein enables to prepare sustainable non-precious metal electrocatalysts with feasible porous characteristics for the AEMFC application.

采用双模板法制备了用于电催化应用的介孔碳 (MC)，并在其中掺杂了钴、铁和氮。制备的材料被用作氧还原反应（ORR）电催化剂和阴离子交换膜燃料电池（AEMFC）的阴极催化剂。MC 材料的制备采用了两种新颖且可持续的酚醛树脂合成路线，同时采用了易于去除的软模板和氧化镁作为硬模板，以获得可行的介孔质地。在双模板中，氧化镁的含量有所不同，以评估其对多孔结构和电催化性能的影响。采用钴和醋酸铁作为过渡金属源，1,10-菲罗啉作为氮源，通过高温热解进行掺杂。物理化学特性分析表明，MC 材料的制备和随后的掺杂都很成功。采用旋转圆盘电极法进行的初步评估表明，合成的催化剂材料在碱性介质中对 ORR 具有极高的电催化活性，并且在 10,000 次电位循环中具有良好的稳定性。在 AEMFC 测试中，最有前途的阴极催化剂显示出卓越的燃料电池性能，峰值功率密度超过 500 mW cm-2，与商用介孔 Fe-N-C 催化剂的性能几乎相同。因此，本文所采用的新颖双模板方法能够制备出具有可行多孔特性的可持续无贵金属电催化剂，用于 AEMFC 应用。

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引用次数: 0

Electrochemical conversion of thin layer amorphous carbon to graphite nanosheets as conductive agents for silicon anode

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-04-11 DOI: 10.1016/j.electacta.2025.146227

Ruoyu Sang , Zesheng Wu , Zhiyong Wang , Xianbo Jin

Silicon is considered as an ideal high-capacity alloy-type anode material for lithium-ion batteries. To address its inherent issues of volume expansion and poor conductivity, various strategies for preparing silicon composite materials have been developed. However, three dimensional porous structured conductive agents may address these two drawbacks simultaneously. In this work, a thin-layer perylenetetracarboxylic dianhydride-derived carbon (PDC) is electrochemically converted into highly crystalline and porous graphite (PDG), which shows about 2.6 times larger pore volume and 28 times higher conductivity than common conductive agent acetylene black (AB). When used as a conductive agent for nanosilicon anodes, PDG endows the electrode with excellent cycling stability and high-rate performance. This work promises a new kind of conductive agents that significantly improve the performance of silicon-based anodes.

硅被认为是锂离子电池理想的高容量合金型负极材料。为了解决硅体积膨胀和导电性差的固有问题，人们开发了各种制备硅复合材料的策略。然而，三维多孔结构导电剂可以同时解决这两个缺点。在这项研究中，薄层过烯四羧酸二酐衍生碳（PDC）通过电化学方法转化为高结晶多孔石墨纳米片（PDG），其孔隙体积比普通导电剂乙炔黑（AB）大约 2.6 倍，导电率则高出 28 倍。当用作纳米硅阳极的导电剂时，PDG 使电极具有出色的循环稳定性和高速性能。这项研究有望开发出一种新型导电剂，显著提高硅基阳极的性能。

引用次数: 0