Pub Date : 2026-02-07DOI: 10.1016/j.electacta.2026.148412
Xiao-Zhong Fan, Xiao-He Zhou, Jin-Hao Zhang, Jin-Xiu Chen, Xiong Xiao, Xiao-Dong Chen, Lin Zhu, Ying-Ze Song, Yu-Zhen Zhao, Long Kong
The pursuit of high energy density batteries necessitates operation at high upper voltages, but exacerbates aluminum (Al) current collector corrosion. Lithium (Li) salts with strong coordination anions in electrolytes could suppress Al corrosion by penetrating the solvation shell of Al3+ and facilitate the Al–anion precipitates due to strong ion–ion interactions. However, such Li salts with strong anion coordination ability encounter starved solubility in carbonate electrolytes. Herein, a sustainable-release of nitrates (NO3−) from a flexible film with an ultrahigh LiNO3 concentration is introduced to circumvent the above dilemma. The fabricated films deliver an extraordinary LiNO3 reserve with an approximately 3.5 folds compared to conventional methods. Therefore, the strong coordination ligands dominate the first solvation shell and prompts the formation of precipitates, which significantly suppress Al corrosion and remarkably demonstrate stable cell operation even at the upper voltage of 4.4 V. Consequently, cell with a high cathode areal capacity (4.5 mAh cm−2, corresponding to 27.5 mg cm−2) achieves over 60 cycles at room temperature and 80 cycles at −20°C. This sustained-release methodology successfully overcomes the inherent solubility constraints of traditional undissolved electrolyte additives, offering a viable pathway for enabling high-voltage lithium-metal batteries with broader electrolyte selections.
追求高能量密度电池需要在高电压下工作，但会加剧铝（Al）集流器的腐蚀。电解质中具有强配位阴离子的锂盐通过穿透Al3+的溶剂化壳层抑制Al腐蚀，并通过强离子-离子相互作用促进Al阴离子析出。然而，这种阴离子配位能力强的锂盐在碳酸盐电解质中存在溶解度不足的问题。本文介绍了一种从具有超高LiNO3浓度的柔性薄膜中持续释放硝酸盐（NO3−）的方法，以避免上述困境。与传统方法相比，制备的薄膜提供了非凡的LiNO3储备，约为3.5倍。因此，强配位体主导了第一溶剂化壳层，促使析出相的形成，显著抑制了Al的腐蚀，即使在4.4 V的高电压下也能表现出稳定的电池运行。因此，具有高阴极面积容量（4.5 mAh cm - 2，相当于27.5 mg cm - 2）的电池在室温下可达到60次以上循环，在- 20°C下可达到80次以上循环。这种缓释方法成功地克服了传统未溶解电解质添加剂固有的溶解度限制，为实现具有更广泛电解质选择的高压锂金属电池提供了可行的途径。
{"title":"Alleviating aluminum corrosion by intensifying lithium nitrate reserves in carbonate electrolytes for high-voltage lithium metal batteries","authors":"Xiao-Zhong Fan, Xiao-He Zhou, Jin-Hao Zhang, Jin-Xiu Chen, Xiong Xiao, Xiao-Dong Chen, Lin Zhu, Ying-Ze Song, Yu-Zhen Zhao, Long Kong","doi":"10.1016/j.electacta.2026.148412","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148412","url":null,"abstract":"The pursuit of high energy density batteries necessitates operation at high upper voltages, but exacerbates aluminum (Al) current collector corrosion. Lithium (Li) salts with strong coordination anions in electrolytes could suppress Al corrosion by penetrating the solvation shell of Al<sup>3+</sup> and facilitate the Al–anion precipitates due to strong ion–ion interactions. However, such Li salts with strong anion coordination ability encounter starved solubility in carbonate electrolytes. Herein, a sustainable-release of nitrates (NO<sub>3</sub><sup>−</sup>) from a flexible film with an ultrahigh LiNO<sub>3</sub> concentration is introduced to circumvent the above dilemma. The fabricated films deliver an extraordinary LiNO<sub>3</sub> reserve with an approximately 3.5 folds compared to conventional methods. Therefore, the strong coordination ligands dominate the first solvation shell and prompts the formation of precipitates, which significantly suppress Al corrosion and remarkably demonstrate stable cell operation even at the upper voltage of 4.4 V. Consequently, cell with a high cathode areal capacity (4.5 mAh cm<sup>−2</sup>, corresponding to 27.5 mg cm<sup>−2</sup>) achieves over 60 cycles at room temperature and 80 cycles at −20°C. This sustained-release methodology successfully overcomes the inherent solubility constraints of traditional undissolved electrolyte additives, offering a viable pathway for enabling high-voltage lithium-metal batteries with broader electrolyte selections.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"1 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135581","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 : 2026-02-07DOI: 10.1016/j.electacta.2026.148400
Victoria Gámez, Natalia García Rey, Antonio Rodes, Víctor Climent, Rosa M. Arán-Ais, Enrique Herrero, Juan M. Feliu
{"title":"Adsorption of methanesulfonate anion on Au(111) and its interaction with water molecules at the electrical double layer","authors":"Victoria Gámez, Natalia García Rey, Antonio Rodes, Víctor Climent, Rosa M. Arán-Ais, Enrique Herrero, Juan M. Feliu","doi":"10.1016/j.electacta.2026.148400","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148400","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"75 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135094","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":"https://doi.org/10.1016/j.electacta.2026.148407","url":null,"abstract":"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.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"211 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","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}
This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through in situ growth of CuCo-MOF nanoflowers on Ti3C2-MXene via a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5-6000 μM), high sensitivity (1408.49 μA mM-1·cm-2), a low detection limit (0.14 μM, S/N=3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.
{"title":"3D porous layered CuCoP/MXene nanoflowers via MXene-assisted in situ growth for non-enzymatic glucose biosensing","authors":"Qiao Wan, Yajun Li, Yahong Su, Wenqing Jia, Jiang Zhu, Qiang Yu, Zhen Chen, Lingli Lei, Yuanyuan Zhang","doi":"10.1016/j.electacta.2026.148403","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148403","url":null,"abstract":"This study aims to develop a high-performance, low-cost non-enzymatic electrochemical sensing materials for glucose detection, addressing the limitations of existing technologies. A three-dimensional porous hierarchical layered-nanoflower heterostructured CuCoP/MXene composite was synthesized through <em>in situ</em> growth of CuCo-MOF nanoflowers on Ti<sub>3</sub>C<sub>2</sub>-MXene <em>via</em> a one-step hydrothermal method, followed by oxidation and phosphidation treatments. This unique architecture significantly increases the specific reactive surface area, exposes abundant active sites, and provides sufficient interfacial regions for glucose oxidation. The synergistic effect between copper (Cu) and cobalt (Co) further enhances the electrocatalytic performance. Meanwhile, MXene serves as a conductive scaffold that not only facilitates electron transfer but also promotes the diffusion and adsorption of glucose molecules, owing to its excellent conductivity and continuous interlayer channels. The fabricated sensor exhibits an extensive linear detection range (0.5-6000 μM), high sensitivity (1408.49 μA mM<sup>-1</sup>·cm<sup>-2</sup>), a low detection limit (0.14 μM, S/N=3), along with excellent selectivity, reproducibility, and stability, together with a swift response time (3 s). Moreover, the sensor has been successfully applied to the accurate detection of glucosein samples of serum, showing high reliability and promising practical value.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"31 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135095","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 : 2026-02-07DOI: 10.1016/j.electacta.2026.148397
Nathanael Brandt, Julia Pross-Brakhage, Jinglin Huang, Hassan Akhtar, Sonia Dsoke, Kai Peter Birke, Lea Eisele, Oliver Fitz
Accurate information about the local pH on electrode surfaces is critical to understand the underlying reaction mechanism and side reactions in Aqueous Zinc-Manganese Dioxide Batteries (AZMBs). Previously reported pH measurements lack sufficient quality and accuracy due to the placement of the pH sensor in the bulk electrolyte and significant excess of electrolyte, which dilutes the pH effects during operation. We present a locally resolved, application‑oriented measurement technique using flat‑tip surface pH sensors placed in direct contact with both electrodes in a setup with minimized electrolyte volumes. The novel pH measurement technique is combined with visual observations from a windowed coin cell operando microscopy setup. In this work, we demonstrate the severity of the cathode-driven pH shifting between 2 and ∼5.5 during cycling in an unbuffered sulfate electrolyte, which induces hydrogen evolution reaction (HER) on the anode, zinc hydroxy-sulfate (ZHS) precipitation at the anode and incomplete ZHS dissolution upon charge. Also, the pH buffering by an acetate-sulfate electrolyte and its limitations with high capacities are investigated. We demonstrate that local pH phenomena influenced by the apparent current density and buffer concentration determine the cell voltage and the onset of HER and ZHS precipitation. The results show the crucial role of the electrolyte composition - controlling both the local and global pH by developing new buffers, cell concepts or adjusted cycling protocols will be essential to make AZMBs an application-ready battery cell technology.
{"title":"Locally Resolved Operando pH Measurement Technique in Aqueous Zinc-Manganese Dioxide Batteries","authors":"Nathanael Brandt, Julia Pross-Brakhage, Jinglin Huang, Hassan Akhtar, Sonia Dsoke, Kai Peter Birke, Lea Eisele, Oliver Fitz","doi":"10.1016/j.electacta.2026.148397","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148397","url":null,"abstract":"Accurate information about the local pH on electrode surfaces is critical to understand the underlying reaction mechanism and side reactions in Aqueous Zinc-Manganese Dioxide Batteries (AZMBs). Previously reported pH measurements lack sufficient quality and accuracy due to the placement of the pH sensor in the bulk electrolyte and significant excess of electrolyte, which dilutes the pH effects during operation. We present a locally resolved, application‑oriented measurement technique using flat‑tip surface pH sensors placed in direct contact with both electrodes in a setup with minimized electrolyte volumes. The novel pH measurement technique is combined with visual observations from a windowed coin cell operando microscopy setup. In this work, we demonstrate the severity of the cathode-driven pH shifting between 2 and ∼5.5 during cycling in an unbuffered sulfate electrolyte, which induces hydrogen evolution reaction (HER) on the anode, zinc hydroxy-sulfate (ZHS) precipitation at the anode and incomplete ZHS dissolution upon charge. Also, the pH buffering by an acetate-sulfate electrolyte and its limitations with high capacities are investigated. We demonstrate that local pH phenomena influenced by the apparent current density and buffer concentration determine the cell voltage and the onset of HER and ZHS precipitation. The results show the crucial role of the electrolyte composition - controlling both the local and global pH by developing new buffers, cell concepts or adjusted cycling protocols will be essential to make AZMBs an application-ready battery cell technology.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"16 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135580","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 : 2026-02-06DOI: 10.1016/j.electacta.2026.148395
Divyansh Anil Khurana, Cyrille Sébert, Philippe M. Vereecken
Nano-semiconductor electrodes are employed for light harvesting applications in (photo-)electrochemical conversion reactions and dye-sensitized solar cells. Accurate determination of their band edge energetic positions is central to their efficacy for isoenergetic charge transfer to the electrolyte. Yet, conventional methods fail for nano-dimensional semiconductor electrodes due to full depletion and extremely small potential-independent space charge widths. In this regard, a new approach was demonstrated on thin film nano-TiO2 electrodes where the current-potential (i-U) characteristics in high and low work function redox probes were interpreted to infer band edge positions in darkness. The methodology is now extended for nano-TiO2 band edge interpretation to illuminated interfaces. Using compact 30 nm TiO2 thin films of both anatase and amorphous phases, we analyze open-circuit potentials and onset potentials in darkness and illumination across varying pH conditions to infer band edge shifts. We also examine temperature rise due to solution heating under illumination from the diffusion-limited currents in the i-U characteristics. Additionally, signatures from surface states in the i-U characteristics are identified, their densities estimated, and their implications discussed. The findings are consolidated through energy band diagrams, offering a comprehensive view of the fully depleted nano-semiconductor/electrolyte interface under operational conditions.
{"title":"Electrochemical redox probes to map light-modulated band edge shifts of nano-TiO2 thin film electrodes in aqueous solutions","authors":"Divyansh Anil Khurana, Cyrille Sébert, Philippe M. Vereecken","doi":"10.1016/j.electacta.2026.148395","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148395","url":null,"abstract":"Nano-semiconductor electrodes are employed for light harvesting applications in (photo-)electrochemical conversion reactions and dye-sensitized solar cells. Accurate determination of their band edge energetic positions is central to their efficacy for isoenergetic charge transfer to the electrolyte. Yet, conventional methods fail for nano-dimensional semiconductor electrodes due to full depletion and extremely small potential-independent space charge widths. In this regard, a new approach was demonstrated on thin film nano-TiO<sub>2</sub> electrodes where the current-potential (i-U) characteristics in high and low work function redox probes were interpreted to infer band edge positions in darkness. The methodology is now extended for nano-TiO<sub>2</sub> band edge interpretation to illuminated interfaces. Using compact 30 nm TiO<sub>2</sub> thin films of both anatase and amorphous phases, we analyze open-circuit potentials and onset potentials in darkness and illumination across varying pH conditions to infer band edge shifts. We also examine temperature rise due to solution heating under illumination from the diffusion-limited currents in the i-U characteristics. Additionally, signatures from surface states in the i-U characteristics are identified, their densities estimated, and their implications discussed. The findings are consolidated through energy band diagrams, offering a comprehensive view of the fully depleted nano-semiconductor/electrolyte interface under operational conditions.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"43 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135092","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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