Sathiya Priya Panjalingam, Somayeh Ahadi, Jakob Michael Hesper, Uta Rodehorst, Sascha Nowak, Birgit Esser, Martin Winter, Peter Bieker
Electrolytes critically influence the electrochemical performance and cycle life of lithium ion batteries (LIBs). This holds especially for organic redox polymer-based batteries, such as those employing poly(3-vinyl-N-methylphenoxazine) (PVMPO), where solubility limits performance in conventional ethylene carbonate (EC)/ dimethyl carbonate (DMC)-based electrolytes. Reducing EC content has shown solubility suppression when using ethyl methyl carbonate (EMC) as a co-solvent, however, capacity fading persists due to PVMPO electrode degradation. To address this degradation, this study explores the use of EC-free electrolytes, with and without fluoroethylene carbonate (FEC). Electrochemical investigations, UltraViolet/Visible (UV/Vis) spectroscopy, post-cycling Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS) mapping, and X-ray Photoelectron Spectroscopy (XPS) analyses are employed to evaluate solubility, interfacial properties, and electrode integrity. The EC-free electrolyte system with FEC retains 95 mAh g‒1, while that without FEC retains 86 mAh g‒1, outperforming the 76 mAh g‒1 observed in EC-based systems after 500 cycles at 1C. FEC containing electrolyte systems display reduced interfacial resistance, fewer surface cracks, and minimal electrode degradation. These findings demonstrate that EC-free electrolytes, particularly with FEC, effectively suppress electrode degradation and enhance the cycle life of organic LIBs.
电解质对锂离子电池的电化学性能和循环寿命有重要影响。这尤其适用于有机氧化还原聚合物基电池,例如使用聚(3-乙烯基- n -甲基苯恶嗪)(PVMPO)的电池,其溶解度限制了传统碳酸乙烯(EC)/碳酸二甲酯(DMC)基电解质的性能。以碳酸甲酯乙酯(EMC)作为共溶剂时,降低EC的含量会抑制其溶解度,但由于PVMPO电极的降解,容量衰退仍然存在。为了解决这种降解问题,本研究探索了不含ec的电解质的使用,包括含和不含氟碳酸乙烯(FEC)的电解质。电化学研究、紫外/可见(UV/Vis)光谱、循环后扫描电子显微镜(SEM)、能量色散x射线能谱(EDS)作图和x射线光电子能谱(XPS)分析用于评估其溶解度、界面性质和电极完整性。含FEC的无ec电解质系统保持95 mAh g-1,而不含FEC的电解质系统保持86 mAh g-1,在1C下循环500次后,优于基于ec的系统的76 mAh g-1。FEC含有电解质系统显示减少的界面电阻,更少的表面裂纹,和最小的电极退化。这些发现表明,不含ec的电解质,特别是含FEC的电解质,有效地抑制了电极的降解,提高了有机lib的循环寿命。
{"title":"Improving Cycle Life and Capacity Retention in PVMPO‖Li Dual-Ion Lithium-Organic Batteries Using an EC-Free and FEC Additive Containing Electrolyte.","authors":"Sathiya Priya Panjalingam, Somayeh Ahadi, Jakob Michael Hesper, Uta Rodehorst, Sascha Nowak, Birgit Esser, Martin Winter, Peter Bieker","doi":"10.1002/smtd.202501766","DOIUrl":"https://doi.org/10.1002/smtd.202501766","url":null,"abstract":"<p><p>Electrolytes critically influence the electrochemical performance and cycle life of lithium ion batteries (LIBs). This holds especially for organic redox polymer-based batteries, such as those employing poly(3-vinyl-N-methylphenoxazine) (PVMPO), where solubility limits performance in conventional ethylene carbonate (EC)/ dimethyl carbonate (DMC)-based electrolytes. Reducing EC content has shown solubility suppression when using ethyl methyl carbonate (EMC) as a co-solvent, however, capacity fading persists due to PVMPO electrode degradation. To address this degradation, this study explores the use of EC-free electrolytes, with and without fluoroethylene carbonate (FEC). Electrochemical investigations, UltraViolet/Visible (UV/Vis) spectroscopy, post-cycling Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS) mapping, and X-ray Photoelectron Spectroscopy (XPS) analyses are employed to evaluate solubility, interfacial properties, and electrode integrity. The EC-free electrolyte system with FEC retains 95 mAh g<sup>‒1</sup>, while that without FEC retains 86 mAh g<sup>‒1</sup>, outperforming the 76 mAh g<sup>‒1</sup> observed in EC-based systems after 500 cycles at 1C. FEC containing electrolyte systems display reduced interfacial resistance, fewer surface cracks, and minimal electrode degradation. These findings demonstrate that EC-free electrolytes, particularly with FEC, effectively suppress electrode degradation and enhance the cycle life of organic LIBs.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01766"},"PeriodicalIF":9.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145964722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Intercalation-based exfoliation offers a cost-effective approach to producing 2D materials. While molecular intercalation surpasses ionic methods in preserving the crystallinity and intrinsic properties of 2D materials, its broader adoption is limited by weak driving forces and slow kinetics. To address these challenges, we propose an interlayer modulation strategy using H3PO4-amine complexes as mediators. Structural and molecular dynamics analyses demonstrate that these complexes regulate interlayer proton activity through strong hydrogen bonding, thereby optimizing interlayer dynamics to enable in situ PW12 formation and efficient graphite exfoliation. The PW12 intercalant shows excellent recyclability via simple alkaline hydrolysis and regeneration, establishing a sustainable route for graphene production. This work overcomes the barrier to molecular intercalation by rationally engineering complex molecular intercalation, achieving universal and high-throughput exfoliation of van der Waals layered materials.
{"title":"Engineering Complex Molecular Intercalation for Efficient, Sustainable Exfoliation of Van Der Waals Layered Materials.","authors":"Zhengyu Wei, Lingzhe Meng, Xue Qin, Faheem Naseem, Wei Wei","doi":"10.1002/smtd.202502143","DOIUrl":"https://doi.org/10.1002/smtd.202502143","url":null,"abstract":"<p><p>Intercalation-based exfoliation offers a cost-effective approach to producing 2D materials. While molecular intercalation surpasses ionic methods in preserving the crystallinity and intrinsic properties of 2D materials, its broader adoption is limited by weak driving forces and slow kinetics. To address these challenges, we propose an interlayer modulation strategy using H<sub>3</sub>PO<sub>4</sub>-amine complexes as mediators. Structural and molecular dynamics analyses demonstrate that these complexes regulate interlayer proton activity through strong hydrogen bonding, thereby optimizing interlayer dynamics to enable in situ PW<sub>12</sub> formation and efficient graphite exfoliation. The PW<sub>12</sub> intercalant shows excellent recyclability via simple alkaline hydrolysis and regeneration, establishing a sustainable route for graphene production. This work overcomes the barrier to molecular intercalation by rationally engineering complex molecular intercalation, achieving universal and high-throughput exfoliation of van der Waals layered materials.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e02143"},"PeriodicalIF":9.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145964775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rasmus S Nielsen, Axel G Medaille, Arnau Torrens, Oriol Segura-Blanch, Seán R Kavanagh, David O Scanlon, Aron Walsh, Edgardo Saucedo, Marcel Placidi, Mirjana Dimitrievska
Selenium is experiencing renewed interest as a elemental semiconductor for a range of optoelectronic and energy applications due to its irresistibly simple composition and favorable wide bandgap. However, its high volatility and low radiative efficiency make it challenging to assess structural and optoelectronic quality, calling for advanced, non-destructive characterization methods. In this work, we employ a closed-space encapsulation strategy to prevent degradation during measurement and enable sensitive probing of vibrational and optoelectronic properties. Using temperature-dependent Raman and photoluminescence spectroscopy, we investigate grown-in stress, vibrational dynamics, and electron-phonon interactions in selenium thin films synthesized under nominally identical conditions across different laboratories. Our results reveal that short-range structural disorder is not intrinsic to the material, but highly sensitive to subtle processing variations, which strongly influence electron-phonon coupling and non-radiative recombination. We find that such structural disorder and grown-in stress likely promote the formation of extended defects, which act as dominant non-radiative recombination centers limiting carrier lifetime and open-circuit voltage in photovoltaic devices. These findings demonstrate that the optoelectronic quality of selenium thin films can be significantly improved through precise control of synthesis and post-deposition treatments, outlining a clear pathway toward optimizing selenium-based thin film technologies through targeted control of crystallization dynamics and microstructural disorder.
{"title":"Spectroscopic Signatures of Structural Disorder and Electron-Phonon Interactions in Trigonal Selenium Thin Films for Solar Energy Harvesting.","authors":"Rasmus S Nielsen, Axel G Medaille, Arnau Torrens, Oriol Segura-Blanch, Seán R Kavanagh, David O Scanlon, Aron Walsh, Edgardo Saucedo, Marcel Placidi, Mirjana Dimitrievska","doi":"10.1002/smtd.202501841","DOIUrl":"https://doi.org/10.1002/smtd.202501841","url":null,"abstract":"<p><p>Selenium is experiencing renewed interest as a elemental semiconductor for a range of optoelectronic and energy applications due to its irresistibly simple composition and favorable wide bandgap. However, its high volatility and low radiative efficiency make it challenging to assess structural and optoelectronic quality, calling for advanced, non-destructive characterization methods. In this work, we employ a closed-space encapsulation strategy to prevent degradation during measurement and enable sensitive probing of vibrational and optoelectronic properties. Using temperature-dependent Raman and photoluminescence spectroscopy, we investigate grown-in stress, vibrational dynamics, and electron-phonon interactions in selenium thin films synthesized under nominally identical conditions across different laboratories. Our results reveal that short-range structural disorder is not intrinsic to the material, but highly sensitive to subtle processing variations, which strongly influence electron-phonon coupling and non-radiative recombination. We find that such structural disorder and grown-in stress likely promote the formation of extended defects, which act as dominant non-radiative recombination centers limiting carrier lifetime and open-circuit voltage in photovoltaic devices. These findings demonstrate that the optoelectronic quality of selenium thin films can be significantly improved through precise control of synthesis and post-deposition treatments, outlining a clear pathway toward optimizing selenium-based thin film technologies through targeted control of crystallization dynamics and microstructural disorder.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01841"},"PeriodicalIF":9.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145964792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maja Dorfner, Anika Mifka, Rodrigo Maia de Pádua, Izabella Thaís da Silva, Iara Zanella Guterres, Lorenzo Sana, Gregor Fuhrmann, Jennifer Munkert
Cancer remains a leading cause of premature mortality worldwide. Targeted drug delivery therapies that selectively attack malignant cells while sparing healthy tissue are essential to minimize side effects and reduce drug dosages. The sodium-potassium ATPase (Na+/K+-ATPase), particularly its catalytic α-subunit, is overexpressed in A549 non-small cell lung cancer (NSCLC) and has thus emerged as a potential therapeutic target. Cardiac glycosides (CGs), plant-derived secondary metabolites, specifically bind and inhibit this enzyme providing target engagement. Coupling CGs to a biocompatible carrier provides a promising new approach for a targeted-orientated drug carrier. Among these nanocarrier systems, cell-derived extracellular vesicles (EVs) gained attention due to their biocompatibility, tumor-targeting capability, and ability to encapsulate compounds. Here, we developed a target-oriented nanocarrier system by linking 3β-azido-3-deoxydigitoxigenin (CA), a semi-synthetic cardenolide derivative, to the surface of A549 cell-derived EVs. The EVs were characterized for particle concentration, size and protein markers. Surface modification was achieved via alkyne modification and click chemistry. Successful conjugation was confirmed by inhibition of the Na+/K+-ATPase activity. Co-localization of CA-modified EVs with the Na+/K+-ATPase was verified by confocal microscopy. Doxorubicin-loaded, CA-modified EVs reduced A549 cell viability to 45% after 48 h, demonstrating its potential use as new drug nanocarrier system.
{"title":"Cardenolide-Engineered Extracellular Vesicles Augment Drug Uptake and Cytotoxicity in Non-small Cell Lung Cancer Cells.","authors":"Maja Dorfner, Anika Mifka, Rodrigo Maia de Pádua, Izabella Thaís da Silva, Iara Zanella Guterres, Lorenzo Sana, Gregor Fuhrmann, Jennifer Munkert","doi":"10.1002/smtd.202501505","DOIUrl":"https://doi.org/10.1002/smtd.202501505","url":null,"abstract":"<p><p>Cancer remains a leading cause of premature mortality worldwide. Targeted drug delivery therapies that selectively attack malignant cells while sparing healthy tissue are essential to minimize side effects and reduce drug dosages. The sodium-potassium ATPase (Na<sup>+</sup>/K<sup>+</sup>-ATPase), particularly its catalytic α-subunit, is overexpressed in A549 non-small cell lung cancer (NSCLC) and has thus emerged as a potential therapeutic target. Cardiac glycosides (CGs), plant-derived secondary metabolites, specifically bind and inhibit this enzyme providing target engagement. Coupling CGs to a biocompatible carrier provides a promising new approach for a targeted-orientated drug carrier. Among these nanocarrier systems, cell-derived extracellular vesicles (EVs) gained attention due to their biocompatibility, tumor-targeting capability, and ability to encapsulate compounds. Here, we developed a target-oriented nanocarrier system by linking 3β-azido-3-deoxydigitoxigenin (CA), a semi-synthetic cardenolide derivative, to the surface of A549 cell-derived EVs. The EVs were characterized for particle concentration, size and protein markers. Surface modification was achieved via alkyne modification and click chemistry. Successful conjugation was confirmed by inhibition of the Na<sup>+</sup>/K<sup>+</sup>-ATPase activity. Co-localization of CA-modified EVs with the Na<sup>+</sup>/K<sup>+</sup>-ATPase was verified by confocal microscopy. Doxorubicin-loaded, CA-modified EVs reduced A549 cell viability to 45% after 48 h, demonstrating its potential use as new drug nanocarrier system.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01505"},"PeriodicalIF":9.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145964768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Correction to: \"Environment-Adaptable Rotational Energy Harvesters Based on Nylon-Core Coiled Carbon Nanotube Yarns\".","authors":"","doi":"10.1002/smtd.70473","DOIUrl":"https://doi.org/10.1002/smtd.70473","url":null,"abstract":"","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e70473"},"PeriodicalIF":9.1,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145964761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dongyu Bai, Junxian Liu, Yihan Nie, Yuantong Gu, Dongchen Qi, Arkady V. Krasheninnikov, Liangzhi Kou
Inside Back Cover
Using density functional theory and deep-learning molecular dynamics, in article number 2500683, Kou and co-workers show that polar domains emerge and can be manipulated in twisted bilayers of ferroelectric CuInP2S6. Their thermal stability and polarization lifetimes are sensitive to twist angle and temperature, and tunable by external electric fields and strain, offering a pathway to control local polarization through rotational manipulation.