Pub Date : 2026-05-01Epub Date: 2026-02-16DOI: 10.1016/j.electacta.2026.148466
Yin-Hung Chen , Zhong-En Shi , Yen-Chen Liu , Bo-Shun Peng , Chao-Kuang Wen , Chih-Lin Wang , Sheng-Chi Chen , Chih-Ping Chen
Interfacial modification of the hole transport layer in perovskite solar cells (PSCs) has recently garnered significant attention for its proven potential to improve device performance. This study systematically compares the structural, chemical, optical, and photovoltaic properties of NiOx thin films deposited by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) under varying oxygen flow ratios (fO2). HiPIMS-deposited NiOx films exhibit a higher Ni³⁺ ratio than DCMS films, leading to more Ni vacancies and lower crystallinity. As hole transport layers in wide bandgap PSCs, both achieved high performances at optimal oxygen flow rates (70 % for DCMS, 50 % for HiPIMS), with HiPIMS slightly outperforming due to reduced interfacial defects, improved charge transport, and suppressed recombination. Incorporating a self-assembled monolayer further boosted performance of wide bandgap PSCs to 20.3 % under one-sun and 40.5 % under 1000 lux indoor lighting, demonstrating strong potential for sustainable, low-light photovoltaics.
{"title":"Comparative study of DCMS and HiPIMS sputtered NiOx thin films for hole transport in wide bandgap perovskite solar cells","authors":"Yin-Hung Chen , Zhong-En Shi , Yen-Chen Liu , Bo-Shun Peng , Chao-Kuang Wen , Chih-Lin Wang , Sheng-Chi Chen , Chih-Ping Chen","doi":"10.1016/j.electacta.2026.148466","DOIUrl":"10.1016/j.electacta.2026.148466","url":null,"abstract":"<div><div>Interfacial modification of the hole transport layer in perovskite solar cells (PSCs) has recently garnered significant attention for its proven potential to improve device performance. This study systematically compares the structural, chemical, optical, and photovoltaic properties of NiO<sub>x</sub> thin films deposited by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) under varying oxygen flow ratios (f<sub>O2</sub>). HiPIMS-deposited NiO<sub>x</sub> films exhibit a higher Ni³⁺ ratio than DCMS films, leading to more Ni vacancies and lower crystallinity. As hole transport layers in wide bandgap PSCs, both achieved high performances at optimal oxygen flow rates (70 % for DCMS, 50 % for HiPIMS), with HiPIMS slightly outperforming due to reduced interfacial defects, improved charge transport, and suppressed recombination. Incorporating a self-assembled monolayer further boosted performance of wide bandgap PSCs to 20.3 % under one-sun and 40.5 % under 1000 lux indoor lighting, demonstrating strong potential for sustainable, low-light photovoltaics.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148466"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146209487","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 : 2026-05-01Epub Date: 2026-02-14DOI: 10.1016/j.electacta.2026.148454
Meng-xia Wang, Lu-jia Deng, Ke-liang Wang, Kun Zou, Ting-hai Yang, Xia Liao, Ren-gui Xiao, Xiang Ke
Artificial solid electrolyte interface (SEI) layers protect lithium (Li) anodes and minimize electrolyte side reactions. Composite SEI layers comprising inorganic and organic materials offer high Li+ conductivity, robust mechanical strength, and excellent flexibility. In this study, Li1.3Al0.3Ti1.7(PO4)3(LATP) is integrated into a matrix of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide) (PEO), lithium bis(trifluoromethanesulfonyl)imide(LiTFSI), and succinonitrile (SN), resulting in the fabrication of composite artificial SEI membranes (PPSL-L16). These membranes consist of a robust inorganic layer (rich in LiF, Li2CO3, and Li3N) and a flexible organic polymer layer. The membranes exhibit high ionic conductivity (σ: 1.40 × 10−3 S cm−1), inhibit Li dendrite formation, and enhance capacity retention and cell cycling stability. After 400 cycles at 1 C, PPSL-L16/Li||LiFePO4 (LFP) full cells retain 88.94 % of their initial capacity—5.64 times that of bare Li (15.77 %)—and the Li anode thickness increases by only 14.4 μm, which is 7 % of that observed in bare Li (205.6 μm), indicating significant suppression of Li dendrite growth. Symmetric PPSL-L16/Li cells achieve stable Li plating/stripping, maintaining a low overpotential (∼100 mV) for 2280 h 0.55 mA cm−2 and 2.1 mA h cm−2. The reduced crystallinity of the complexes and interfacial modulation by LATP enhance Li+ transport, thereby improving the σ of the composite SEI, broadening its electrochemical stability window (ESW), and further suppressing Li dendrite formation. These improvements contribute to superior battery safety, cycling performance, and rate capability. This strategy provides a feasible and effective approach for developing high-performance Li-metal batteries with long cycle life.
人工固体电解质界面（SEI）层保护锂（Li）阳极，并最大限度地减少电解质副反应。由无机和有机材料组成的复合SEI层具有高Li+导电性，坚固的机械强度和优异的柔韧性。本研究将Li1.3Al0.3Ti1.7(PO4)3（LATP）集成到聚偏氟乙烯-共六氟丙烯（PVDF-HFP）、聚环氧乙烷（PEO）、双（三氟甲烷磺酰）亚胺锂（LiTFSI）和丁二腈（SN）的基体中，制备了复合人工SEI膜（PPSL-L16）。这些膜由坚固的无机层（富含LiF， Li2CO3和Li3N）和柔性的有机聚合物层组成。该膜具有高离子电导率（σ: 1.40 × 10−3 S cm−1），抑制锂枝晶的形成，提高容量保持和细胞循环稳定性。在1℃下循环400次后，PPSL-L16/Li||LiFePO4 （LFP）满电池保留了其初始容量的88.94%，是裸锂电池（15.77%）的5.64倍，而锂阳极厚度仅增加了14.4 μm，是裸锂电池（205.6 μm）的7%，表明锂枝晶生长受到了显著抑制。对称的PPSL-L16/Li电池实现了稳定的锂电镀/剥离，在0.55 mA cm - 2和2.1 mA h cm - 2的2280小时内保持低过电位（~ 100 mV）。配合物结晶度的降低和LATP的界面调制增强了Li+的输运，从而提高了复合材料SEI的σ，扩大了其电化学稳定窗口（ESW），进一步抑制了Li枝晶的形成。这些改进有助于提高电池的安全性、循环性能和倍率能力。该策略为开发长循环寿命高性能锂金属电池提供了可行有效的途径。
{"title":"Design and construction of organic-inorganic composite artificial solid electrolyte interface films with high ionic conductivity for lithium-metal batteries","authors":"Meng-xia Wang, Lu-jia Deng, Ke-liang Wang, Kun Zou, Ting-hai Yang, Xia Liao, Ren-gui Xiao, Xiang Ke","doi":"10.1016/j.electacta.2026.148454","DOIUrl":"10.1016/j.electacta.2026.148454","url":null,"abstract":"<div><div>Artificial solid electrolyte interface (SEI) layers protect lithium (Li) anodes and minimize electrolyte side reactions. Composite SEI layers comprising inorganic and organic materials offer high Li<sup>+</sup> conductivity, robust mechanical strength, and excellent flexibility. In this study, Li<sub>1.3</sub>Al<sub>0.3</sub>Ti<sub>1.7</sub>(PO<sub>4</sub>)<sub>3</sub>(LATP) is integrated into a matrix of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide) (PEO), lithium bis(trifluoromethanesulfonyl)imide(LiTFSI), and succinonitrile (SN), resulting in the fabrication of composite artificial SEI membranes (PPSL-L16). These membranes consist of a robust inorganic layer (rich in LiF, Li<sub>2</sub>CO<sub>3</sub>, and Li<sub>3</sub>N) and a flexible organic polymer layer. The membranes exhibit high ionic conductivity (σ: 1.40 × 10<sup>−3</sup> S cm<sup>−1</sup>), inhibit Li dendrite formation, and enhance capacity retention and cell cycling stability. After 400 cycles at 1 C, PPSL-L16/Li||LiFePO<sub>4</sub> (LFP) full cells retain 88.94 % of their initial capacity—5.64 times that of bare Li (15.77 %)—and the Li anode thickness increases by only 14.4 μm, which is 7 % of that observed in bare Li (205.6 μm), indicating significant suppression of Li dendrite growth. Symmetric PPSL-L16/Li cells achieve stable Li plating/stripping, maintaining a low overpotential (∼100 mV) for 2280 h 0.55 mA cm<sup>−2</sup> and 2.1 mA h cm<sup>−2</sup>. The reduced crystallinity of the complexes and interfacial modulation by LATP enhance Li<sup>+</sup> transport, thereby improving the σ of the composite SEI, broadening its electrochemical stability window (ESW), and further suppressing Li dendrite formation. These improvements contribute to superior battery safety, cycling performance, and rate capability. This strategy provides a feasible and effective approach for developing high-performance Li-metal batteries with long cycle life.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148454"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146209581","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 : 2026-05-01Epub Date: 2026-02-23DOI: 10.1016/j.electacta.2026.148463
Zsolt Szakály, Gábor János Szirtes, Soma Vesztergom
A fast, robust, and low-error method is described for the simulation of transient diffusion in electrochemical systems, particularly those featuring complex, high surface area geometries in one, two, or three dimensions—like porous electrode structures used in electrocatalysis. Our approach reformulates the discrete solution of Fick’s laws by approximating the propagation matrix with a Gaussian convolution kernel. This methodology leverages the known spectral decomposition of symmetric tridiagonal matrices, significantly reducing computational cost compared to traditional methods that rely on large-scale matrix inversion or exponentiation. Furthermore, this method is highly amenable to parallelization and GPU acceleration. We detail the implementation of various electrochemical boundary conditions, including diffusion control and mixed kinetic-diffusion control, demonstrating the potential of the method as a fast, user-friendly, and powerful tool for electrochemical simulations.
{"title":"A convolutional kernel approach for efficient simulation of diffusion in complex electrode geometries","authors":"Zsolt Szakály, Gábor János Szirtes, Soma Vesztergom","doi":"10.1016/j.electacta.2026.148463","DOIUrl":"10.1016/j.electacta.2026.148463","url":null,"abstract":"<div><div>A fast, robust, and low-error method is described for the simulation of transient diffusion in electrochemical systems, particularly those featuring complex, high surface area geometries in one, two, or three dimensions—like porous electrode structures used in electrocatalysis. Our approach reformulates the discrete solution of Fick’s laws by approximating the propagation matrix with a Gaussian convolution kernel. This methodology leverages the known spectral decomposition of symmetric tridiagonal matrices, significantly reducing computational cost compared to traditional methods that rely on large-scale matrix inversion or exponentiation. Furthermore, this method is highly amenable to parallelization and GPU acceleration. We detail the implementation of various electrochemical boundary conditions, including diffusion control and mixed kinetic-diffusion control, demonstrating the potential of the method as a fast, user-friendly, and powerful tool for electrochemical simulations.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148463"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146777950","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}
Electrochemically generated radical anions (R•−) of several polycyclic aromatic hydrocarbons (R) were used for the surface treatment of polytetrafluoroethylene (PTFE). R•− works as an electron donor, which causes reductive elimination of F− on the PTFE surface. It was shown that the reduction potential of R significantly affects the rate of the reductive elimination of F−. By the reductive treatment of the PTFE surface, the contact angle of a water droplet decreased from 110° to about 60°. The contact angle change was analyzed to determine a standard rate constant of the reductive elimination (k0) with the radical anion of pyrene (Py•−) and anthracene (An•−), based on the Butler-Volmer model, and k0 = 5.7 × 10−4 and 4.6 × 10−4 M−1 s−1 for An•− and Py•−, respectively, were obtained. Furthermore, electroless deposition of Au and Cu on the treated PTFE sheets was carried out. Due to the reductive surface treatment, the Au and Cu layer was formed more uniformly than in the case of the untreated PTFE by the electroless deposition.
{"title":"Reductive surface treatment of polytetrafluoroethylene with electrochemically generated radical anions of several polycyclic aromatic hydrocarbons","authors":"Shogo Kawashima , Arata Nagashima , Yojiro Yamamoto , Hiroshi Shiigi , Ryoichi Ishimatsu","doi":"10.1016/j.electacta.2026.148407","DOIUrl":"10.1016/j.electacta.2026.148407","url":null,"abstract":"<div><div>Electrochemically generated radical anions (R<sup>•−</sup>) of several polycyclic aromatic hydrocarbons (R) were used for the surface treatment of polytetrafluoroethylene (PTFE). R<sup>•−</sup> works as an electron donor, which causes reductive elimination of F<sup>−</sup> on the PTFE surface. It was shown that the reduction potential of R significantly affects the rate of the reductive elimination of F<sup>−</sup>. By the reductive treatment of the PTFE surface, the contact angle of a water droplet decreased from 110° to about 60°. The contact angle change was analyzed to determine a standard rate constant of the reductive elimination (<em>k</em><sup>0</sup>) with the radical anion of pyrene (Py<sup>•−</sup>) and anthracene (An<sup>•−</sup>), based on the Butler-Volmer model, and <em>k</em><sup>0</sup> = 5.7 × 10<sup>−4</sup> and 4.6 × 10<sup>−4</sup> M<sup>−1</sup> s<sup>−1</sup> for An<sup>•−</sup> and Py<sup>•−</sup>, respectively, were obtained. Furthermore, electroless deposition of Au and Cu on the treated PTFE sheets was carried out. Due to the reductive surface treatment, the Au and Cu layer was formed more uniformly than in the case of the untreated PTFE by the electroless deposition.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148407"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135584","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 : 2026-05-01Epub Date: 2026-02-14DOI: 10.1016/j.electacta.2026.148458
Yue He , Yadong Zhu , Jianshu Wang , Shihui Huang , Yuke Liu , Baohong Gao
With the continuous scaling down of integrated circuit (IC) feature sizes, the demand for interconnect planarization has become increasingly stringent. Chemical mechanical polishing (CMP) has emerged as a critical enabling technology for achieving high-density integration and multi-level interconnects. However, during the CMP process, the issue of galvanic corrosion between Cu interconnects and barrier layer metals has become increasingly prominent, posing a significant challenge to IC performance and reliability. This corrosion phenomenon can lead to increased electrical resistance, non-uniform current density distribution, and accelerated failures such as electromigration and stress migration. Consequently, a thorough investigation of galvanic corrosion behavior during Cu CMP and the development of effective mitigation strategies are of paramount importance for advancing IC manufacturing technology. This review systematically elucidates the formation mechanisms and control strategies for galvanic corrosion between copper interconnect layers and barrier layer metals during CMP. It summarizes mainstream electrochemical methods employed for detecting this corrosion behavior and reviews the current state of research on modulating galvanic corrosion for different barrier metals through slurry component optimization. Thereby, an integrated "mechanism-detection-mitigation" analytical framework is constructed. This article aims to provide theoretical reference and practical guidance for researchers in the IC manufacturing field, fostering a deeper understanding and more effective control of galvanic corrosion issues in copper interconnect CMP, ultimately contributing to the sustained advancement of integrated circuit technology.
{"title":"Research progress on galvanic corrosion mechanisms and suppression strategies in Cu interconnect CMP processes for IC","authors":"Yue He , Yadong Zhu , Jianshu Wang , Shihui Huang , Yuke Liu , Baohong Gao","doi":"10.1016/j.electacta.2026.148458","DOIUrl":"10.1016/j.electacta.2026.148458","url":null,"abstract":"<div><div>With the continuous scaling down of integrated circuit (IC) feature sizes, the demand for interconnect planarization has become increasingly stringent. Chemical mechanical polishing (CMP) has emerged as a critical enabling technology for achieving high-density integration and multi-level interconnects. However, during the CMP process, the issue of galvanic corrosion between Cu interconnects and barrier layer metals has become increasingly prominent, posing a significant challenge to IC performance and reliability. This corrosion phenomenon can lead to increased electrical resistance, non-uniform current density distribution, and accelerated failures such as electromigration and stress migration. Consequently, a thorough investigation of galvanic corrosion behavior during Cu CMP and the development of effective mitigation strategies are of paramount importance for advancing IC manufacturing technology. This review systematically elucidates the formation mechanisms and control strategies for galvanic corrosion between copper interconnect layers and barrier layer metals during CMP. It summarizes mainstream electrochemical methods employed for detecting this corrosion behavior and reviews the current state of research on modulating galvanic corrosion for different barrier metals through slurry component optimization. Thereby, an integrated \"mechanism-detection-mitigation\" analytical framework is constructed. This article aims to provide theoretical reference and practical guidance for researchers in the IC manufacturing field, fostering a deeper understanding and more effective control of galvanic corrosion issues in copper interconnect CMP, ultimately contributing to the sustained advancement of integrated circuit technology.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148458"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146209540","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 : 2026-05-01Epub Date: 2026-02-19DOI: 10.1016/j.electacta.2026.148501
Yingshi Su , Sijie Chen , Weiran Zheng
Fluorine-doped tin oxide (FTO) is a cornerstone transparent conducting oxide in electrochemistry and materials science, yet its stability is often assumed rather than verified. This work presents a time-resolved operando investigation into the degradation of the FTO electrode, quantitatively mapping its chemical and electrochemical stability in acidic (0.5 M H2SO4), neutral (1.0 M KCl), and alkaline (1.0 M KOH) environments. By employing time-resolved electrochemical impedance analysis and cyclic voltammetry-coupled electrochemical impedance spectroscopy protocol, we simultaneously track changes in FTO resistance and double-layer capacitance to deconvolve distinct degradation mechanisms. Our findings reveal that FTO stability is highly conditional. Alkaline media are universally corrosive, causing severe surface roughening (capacitance increases >90 %) and conductivity loss even during simple chemical immersion. In contrast, under acidic and neutral conditions, cathodic cycling drives surface roughening, whereas anodic cycling leads to surface smoothing. Most notably, the impact on conductivity is potential-specific: anodic polarization improves conductivity in neutral KCl but is destructive in KOH, where stannate (SnO32−) formation causes the largest rise in resistance (+7.3 %). By correlating electrical parameters with specific redox processes, this study provides a quantitative framework for understanding FTO degradation and establishes critical operating windows to ensure FTO reliability in electrochemical applications.
氟掺杂氧化锡（FTO）是电化学和材料科学领域的基础透明导电氧化物，但其稳定性往往是假设而不是验证。这项工作对FTO电极的降解进行了时间分辨的operando研究，定量绘制了其在酸性（0.5 M H2SO4）、中性（1.0 M KCl）和碱性（1.0 M KOH）环境下的化学和电化学稳定性。通过时间分辨电化学阻抗分析和循环伏安耦合电化学阻抗谱，我们同时跟踪FTO电阻和双层电容的变化，以反卷积不同的降解机制。我们的研究结果表明，FTO稳定性是高度有条件的。碱性介质普遍具有腐蚀性，即使在简单的化学浸泡中也会导致严重的表面粗糙化（电容增加90%）和电导率损失。相反，在酸性和中性条件下，阴极循环驱动表面粗化，而阳极循环导致表面光滑。最值得注意的是，对电导率的影响是电位特异性的：阳极极化提高了中性KCl中的电导率，但在KOH中是破坏性的，其中锡酸盐（SnO32−）的形成导致电阻最大的上升（+7.3%）。通过将电参数与特定氧化还原过程相关联，本研究为理解FTO降解提供了定量框架，并建立了关键操作窗口，以确保FTO在电化学应用中的可靠性。
{"title":"Time-resolved analysis of the FTO surface dynamics in aqueous solution","authors":"Yingshi Su , Sijie Chen , Weiran Zheng","doi":"10.1016/j.electacta.2026.148501","DOIUrl":"10.1016/j.electacta.2026.148501","url":null,"abstract":"<div><div>Fluorine-doped tin oxide (FTO) is a cornerstone transparent conducting oxide in electrochemistry and materials science, yet its stability is often assumed rather than verified. This work presents a time-resolved operando investigation into the degradation of the FTO electrode, quantitatively mapping its chemical and electrochemical stability in acidic (0.5 M H<sub>2</sub>SO<sub>4</sub>), neutral (1.0 M KCl), and alkaline (1.0 M KOH) environments. By employing time-resolved electrochemical impedance analysis and cyclic voltammetry-coupled electrochemical impedance spectroscopy protocol, we simultaneously track changes in FTO resistance and double-layer capacitance to deconvolve distinct degradation mechanisms. Our findings reveal that FTO stability is highly conditional. Alkaline media are universally corrosive, causing severe surface roughening (capacitance increases >90 %) and conductivity loss even during simple chemical immersion. In contrast, under acidic and neutral conditions, cathodic cycling drives surface roughening, whereas anodic cycling leads to surface smoothing. Most notably, the impact on conductivity is potential-specific: anodic polarization improves conductivity in neutral KCl but is destructive in KOH, where stannate (SnO<sub>3</sub><sup>2−</sup>) formation causes the largest rise in resistance (+7.3 %). By correlating electrical parameters with specific redox processes, this study provides a quantitative framework for understanding FTO degradation and establishes critical operating windows to ensure FTO reliability in electrochemical applications.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148501"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146261152","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 : 2026-05-01Epub Date: 2026-02-22DOI: 10.1016/j.electacta.2026.148514
Ugur Caglayan
In this study, boron-doped and hybrid carbon/titanium (C/Ti) surface modified LiFePO4 cathode materials were synthesized via hydrothermal methods to overcome the low intrinsic kinetic conductivity and surface instability of LiFePO4. The synergy between bulk boron doping and the surface C/Ti coating was systematically investigated through structural and electrochemical characterizations. Structural analyses showed that B3+ ions successfully incorporated into the P5+ regions, leading to lattice contraction and the formation of oxygen vacancies, which significantly improved Li+ diffusion kinetics. Simultaneously, the titanium-based interphase acted as a robust protective layer that minimized electrolyte side reactions and maintained structural integrity in long-term cycling. Electrochemical results revealed that the optimized LFP_2B@CTi sample exhibited a low charge transfer resistance of 98.2 Ω and maintained a high discharge capacity of 102 mAh/g at a high rate of 5C. Furthermore, the material exhibited a Coulombic efficiency of 96.24% after 200 cycles at 0.5 C, proving that capacity degradation mechanisms were suppressed. These results demonstrated that the proposed dual modification strategy offers a highly promising pathway for developing high-performance cathode material for high-power lithium-ion battery applications by providing a strong synergistic effect.
{"title":"Synergistic effects of LiFePO4 cathodes via B-doping and C/Ti hybrid coating for enhanced electrochemical performance","authors":"Ugur Caglayan","doi":"10.1016/j.electacta.2026.148514","DOIUrl":"10.1016/j.electacta.2026.148514","url":null,"abstract":"<div><div>In this study, boron-doped and hybrid carbon/titanium (C/Ti) surface modified LiFePO<sub>4</sub> cathode materials were synthesized via hydrothermal methods to overcome the low intrinsic kinetic conductivity and surface instability of LiFePO<sub>4</sub>. The synergy between bulk boron doping and the surface C/Ti coating was systematically investigated through structural and electrochemical characterizations. Structural analyses showed that B<sup>3+</sup> ions successfully incorporated into the P<sup>5+</sup> regions, leading to lattice contraction and the formation of oxygen vacancies, which significantly improved Li<sup>+</sup> diffusion kinetics. Simultaneously, the titanium-based interphase acted as a robust protective layer that minimized electrolyte side reactions and maintained structural integrity in long-term cycling. Electrochemical results revealed that the optimized LFP_2B@CTi sample exhibited a low charge transfer resistance of 98.2 Ω and maintained a high discharge capacity of 102 mAh/g at a high rate of 5C. Furthermore, the material exhibited a Coulombic efficiency of 96.24% after 200 cycles at 0.5 C, proving that capacity degradation mechanisms were suppressed. These results demonstrated that the proposed dual modification strategy offers a highly promising pathway for developing high-performance cathode material for high-power lithium-ion battery applications by providing a strong synergistic effect.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148514"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146777958","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 : 2026-05-01Epub Date: 2026-02-20DOI: 10.1016/j.electacta.2026.148502
Li Zhao , Xiao Yu , Zhengshao Xiong , Kun Wang , Ran Cui , Zihan Wang , Yang Li , Yang Lei
Conjugated microporous polymers (CMPs) are often hampered by intrinsic structural disorder, which leads to a critical trade-off among electrical conductivity, ion accessibility, and active site utilization, thereby creating a kinetic disparity between Faradaic reactions and charge transport. Here, we report a molecular anchoring strategy that guides a transition from amorphous to partially crystalline order within a CMPs framework. This is achieved through a “radial coordination-axial covalent” design, wherein the synergistic effect between rigid pyrene planes and Co-N/O coordination geometry acts as a molecular anchor, directing ordered polymer packing. Co-N2O2 coordination centers are constructed to narrow the bandgap via d-π orbital hybridization and provide highly active Faradaic reaction sites. Concurrently, the axial covalent grafting of this coordinated framework onto single-walled carbon nanotubes (SWCNTs) constructs a core-shell heterostructure, which establishes continuous electron pathways and hierarchical mass transfer channels. As a result, the Py-Co-Salen-CMP@SWCNTs composite demonstrates an exceptional three-electrode specific capacitance of 1131.5 F g-1 at 0.5 A g-1 and maintaining 93 % capacitance retention after 5000 cycles. A symmetric two-electrode supercapacitor based on Py-Co-Salen-CMP@SWCNTs achieves a specific capacitance of 452 F g-1 within a 1 V voltage window, delivering a high energy density of 62.78 W h kg-1 and maintaining 91.1 % capacitance retention. This work demonstrates that molecular anchoring-induced structural ordering combined with interfacial engineering is an effective strategy to unlock the potential of CMPs for high-performance energy storage.
共轭微孔聚合物（cmp）通常受到固有结构紊乱的阻碍，这导致电导率，离子可及性和活性位点利用之间的关键权衡，从而在法拉第反应和电荷传输之间产生动力学差异。在这里，我们报告了一种分子锚定策略，可以在CMPs框架内引导从无定形到部分结晶顺序的转变。这是通过“径向配位-轴向共价”设计实现的，其中刚性芘平面和Co-N/O配位几何之间的协同效应作为分子锚点，指导有序的聚合物填充。通过d-π轨道杂化，构建Co-N2O2配位中心来缩小带隙，并提供高活性的法拉第反应位点。同时，将该配位框架轴向共价接枝到单壁碳纳米管（SWCNTs）上，构建了核壳异质结构，建立了连续的电子路径和分层的传质通道。因此，Py-Co-Salen-CMP@SWCNTs复合材料在0.5 a g-1下具有1131.5 F -1的特殊三电极比电容，并在5000次循环后保持93%的电容保持率。基于Py-Co-Salen-CMP@SWCNTs的对称双电极超级电容器在1 V电压窗内可实现452 F -1的比电容，提供62.78 W h kg-1的高能量密度，并保持91.1%的电容保持率。这项工作表明，分子锚定诱导的结构排序与界面工程相结合是释放cmp高性能储能潜力的有效策略。
{"title":"Engineering rapid charge storage: Building electron-ion dual highways in CMP/SWCNT electrodes through cobalt coordination and covalent grafting","authors":"Li Zhao , Xiao Yu , Zhengshao Xiong , Kun Wang , Ran Cui , Zihan Wang , Yang Li , Yang Lei","doi":"10.1016/j.electacta.2026.148502","DOIUrl":"10.1016/j.electacta.2026.148502","url":null,"abstract":"<div><div>Conjugated microporous polymers (CMPs) are often hampered by intrinsic structural disorder, which leads to a critical trade-off among electrical conductivity, ion accessibility, and active site utilization, thereby creating a kinetic disparity between Faradaic reactions and charge transport. Here, we report a molecular anchoring strategy that guides a transition from amorphous to partially crystalline order within a CMPs framework. This is achieved through a “radial coordination-axial covalent” design, wherein the synergistic effect between rigid pyrene planes and Co-N/O coordination geometry acts as a molecular anchor, directing ordered polymer packing. Co-N<sub>2</sub>O<sub>2</sub> coordination centers are constructed to narrow the bandgap via <span>d</span>-π orbital hybridization and provide highly active Faradaic reaction sites. Concurrently, the axial covalent grafting of this coordinated framework onto single-walled carbon nanotubes (SWCNTs) constructs a core-shell heterostructure, which establishes continuous electron pathways and hierarchical mass transfer channels. As a result, the Py-Co-Salen-CMP@SWCNTs composite demonstrates an exceptional three-electrode specific capacitance of 1131.5 F g<sup>-1</sup> at 0.5 A g<sup>-1</sup> and maintaining 93 % capacitance retention after 5000 cycles. A symmetric two-electrode supercapacitor based on Py-Co-Salen-CMP@SWCNTs achieves a specific capacitance of 452 F g<sup>-1</sup> within a 1 V voltage window, delivering a high energy density of 62.78 W h kg<sup>-1</sup> and maintaining 91.1 % capacitance retention. This work demonstrates that molecular anchoring-induced structural ordering combined with interfacial engineering is an effective strategy to unlock the potential of CMPs for high-performance energy storage.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148502"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146778425","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 : 2026-05-01Epub Date: 2026-02-13DOI: 10.1016/j.electacta.2026.148449
Leonardo D. Robledo Candia, Gabriel C. Lavorato, Aldo A. Rubert, Mariano H. Fonticelli
The stability of metal nanoparticles (NPs) determines their performance in applications ranging from catalysis to biomedicine. When metal NPs can exchange charge with ionic species in an electrolyte, smaller particles oxidize while larger ones grow, undergoing electrochemical Ostwald ripening (EOR). This process is driven by differences in excess surface free energy, described by the Gibbs-Thomson (GT) relation. We develop a theoretical framework to predict the evolution of NP size distributions when oxidation and reduction rates are controlled by charge-transfer kinetics at the nanoparticle/electrolyte interface. Under these conditions, the system naturally develops a time dependent mixed potential that governs its temporal evolution. Computational simulations show that the long-time behavior of EOR follows the power-law growth of the mean particle size predicted by the Lifshitz–Slyozov–Wagner (LSW) theory for surface-controlled ripening (SCR). However, EOR produces distinctive skewness and broader distributions. We show that most deviations from SCR originate from the linearization of the GT relation in traditional LSW approaches, which becomes inaccurate for small NPs. Furthermore, the long-time polydispersity index in EOR exceeds that of diffusion-controlled ripening, indicating intrinsically broader distributions under electrochemical control. These results provide key insights into the coarsening pathways of metal NPs during their synthesis, storage, and electrochemical operation.
{"title":"Intrinsic nature of electrochemical Ostwald ripening: Spontaneous size-distribution evolution without external bias","authors":"Leonardo D. Robledo Candia, Gabriel C. Lavorato, Aldo A. Rubert, Mariano H. Fonticelli","doi":"10.1016/j.electacta.2026.148449","DOIUrl":"10.1016/j.electacta.2026.148449","url":null,"abstract":"<div><div>The stability of metal nanoparticles (NPs) determines their performance in applications ranging from catalysis to biomedicine. When metal NPs can exchange charge with ionic species in an electrolyte, smaller particles oxidize while larger ones grow, undergoing electrochemical Ostwald ripening (EOR). This process is driven by differences in excess surface free energy, described by the Gibbs-Thomson (GT) relation. We develop a theoretical framework to predict the evolution of NP size distributions when oxidation and reduction rates are controlled by charge-transfer kinetics at the nanoparticle/electrolyte interface. Under these conditions, the system naturally develops a time dependent mixed potential that governs its temporal evolution. Computational simulations show that the long-time behavior of EOR follows the power-law growth of the mean particle size predicted by the Lifshitz–Slyozov–Wagner (LSW) theory for surface-controlled ripening (SCR). However, EOR produces distinctive skewness and broader distributions. We show that most deviations from SCR originate from the linearization of the GT relation in traditional LSW approaches, which becomes inaccurate for small NPs. Furthermore, the long-time polydispersity index in EOR exceeds that of diffusion-controlled ripening, indicating intrinsically broader distributions under electrochemical control. These results provide key insights into the coarsening pathways of metal NPs during their synthesis, storage, and electrochemical operation.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148449"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184256","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 : 2026-05-01Epub Date: 2026-02-18DOI: 10.1016/j.electacta.2026.148474
Xueying Lu , Xu Han , Dan Zhao , Tianhao Wang , Yinan Liu , Jing Hu , Yitao He
Hydrogen energy, featuring high energy density and environmental friendliness, is a highly promising renewable clean energy carrier. Electrolytic water splitting for hydrogen production is effective for high-purity H2, with efficient and stable electrocatalysts being the key to efficiency optimization. Rhenium-based catalysts attract attention due to their unique electronic structure, high activity, and broad pH adaptability, but enhancing their hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance remains a challenge. This study reports a two-step hydrothermal method to in situ grow Co9S8-ReS2Ni3S2 on nickel foam. Co incorporation induces “coral-like” nanostructures, increasing active surface area and suppressing agglomeration, while strong ReS2Co9S8 interfacial coupling optimizes charge redistribution. The catalyst exhibits overpotentials of 89 mV (HER) and 268 mV (OER) at 10 mA cm-2, achieves 10 mA cm-2 at 1.61 V for overall water splitting, and maintains stability for 100 h, providing new insights for high-performance electrocatalysts.
氢能具有能量密度高、环境友好等特点，是一种极具发展前景的可再生清洁能源载体。电解水裂解制氢是制备高纯氢气的有效方法，高效稳定的电催化剂是优化效率的关键。铼基催化剂因其独特的电子结构、高活性和广泛的pH适应性而备受关注，但提高其析氢反应（HER）和析氧反应（OER）性能仍然是一个挑战。本研究采用两步水热法在泡沫镍（NF）上原位生长Co9S8-ReS2-Ni3S2/NF。Co的掺入诱导了“珊瑚状”纳米结构，增加了活性表面积，抑制了团聚，而强ReS2-Co9S8界面耦合优化了电荷再分配。该催化剂在10 mA cm-2时表现出89 mV （HER）和268 mV （OER）的过电位，在1.61 V时达到10 mA cm-2，并保持100 h的稳定性，为高性能电催化剂提供了新的见解。
{"title":"Construction of Co9S8-ReS2Ni3S2/NF catalyst and its electrocatalytic water splitting performance","authors":"Xueying Lu , Xu Han , Dan Zhao , Tianhao Wang , Yinan Liu , Jing Hu , Yitao He","doi":"10.1016/j.electacta.2026.148474","DOIUrl":"10.1016/j.electacta.2026.148474","url":null,"abstract":"<div><div>Hydrogen energy, featuring high energy density and environmental friendliness, is a highly promising renewable clean energy carrier. Electrolytic water splitting for hydrogen production is effective for high-purity H<sub>2</sub>, with efficient and stable electrocatalysts being the key to efficiency optimization. Rhenium-based catalysts attract attention due to their unique electronic structure, high activity, and broad pH adaptability, but enhancing their hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance remains a challenge. This study reports a two-step hydrothermal method to in situ grow Co<sub>9</sub>S<sub>8</sub>-ReS<sub>2<img></sub>Ni<sub>3</sub>S<sub>2</sub> on nickel foam. Co incorporation induces “coral-like” nanostructures, increasing active surface area and suppressing agglomeration, while strong ReS<sub>2<img></sub>Co<sub>9</sub>S<sub>8</sub> interfacial coupling optimizes charge redistribution. The catalyst exhibits overpotentials of 89 mV (HER) and 268 mV (OER) at 10 mA cm<sup>-2</sup>, achieves 10 mA cm<sup>-2</sup> at 1.61 V for overall water splitting, and maintains stability for 100 h, providing new insights for high-performance electrocatalysts.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"557 ","pages":"Article 148474"},"PeriodicalIF":5.6,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223365","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号