Noah Al-Shamery, Dimitrios Valavanis, Bethanie Dean, Anna Dettlaff, Michał Sobaszek, Robert Bogdanowicz, Paul Wilson, Pooi See Lee, Patrick R Unwin
Scanning electrochemical cell microscopy (SECCM) is a versatile tool for localized electrochemical mapping, material modification, and microfabrication. In its hopping mode, the pipette-based system confines reactions to the meniscus contact area, allowing precise deposition control. Here, an SECCM-driven strategy for polypyrrole (PPy) microfabrication using phosphate buffer as the electrolyte, combined with an intermediate cleaning step to remove side products and prevent pipette clogging, is reported. This approach enables the production of uniform, circular PPy deposits with high reproducibility on gold substrates. A multi-microscopy "conveyor-belt" analysis - combining SEM, AFM, EDX, and Raman spectroscopy - reveals that phosphate ions intercalate into the PPy matrix during polymerization, as also seen in bulk studies. This intercalation is found to be reversible via post-deposition rinsing. Furthermore, this work demonstrates that cyclic voltammetry-based deposition enables patterned PPy growth on complex surfaces such as boron-doped carbon nanowalls, overcoming surface charge and wetting challenges. These findings expand the applicability of SECCM for 2D conducting polymer micro-/nanofabrication on both flat and structurally complex substrates.
{"title":"Optimizing Electrochemical Microprinting of Conducting Polymers: Scanning Electrochemical Cell Microscopy (SECCM) Coupled with Conveyor-Belt Surface Analysis.","authors":"Noah Al-Shamery, Dimitrios Valavanis, Bethanie Dean, Anna Dettlaff, Michał Sobaszek, Robert Bogdanowicz, Paul Wilson, Pooi See Lee, Patrick R Unwin","doi":"10.1002/smtd.202501781","DOIUrl":"https://doi.org/10.1002/smtd.202501781","url":null,"abstract":"<p><p>Scanning electrochemical cell microscopy (SECCM) is a versatile tool for localized electrochemical mapping, material modification, and microfabrication. In its hopping mode, the pipette-based system confines reactions to the meniscus contact area, allowing precise deposition control. Here, an SECCM-driven strategy for polypyrrole (PPy) microfabrication using phosphate buffer as the electrolyte, combined with an intermediate cleaning step to remove side products and prevent pipette clogging, is reported. This approach enables the production of uniform, circular PPy deposits with high reproducibility on gold substrates. A multi-microscopy \"conveyor-belt\" analysis - combining SEM, AFM, EDX, and Raman spectroscopy - reveals that phosphate ions intercalate into the PPy matrix during polymerization, as also seen in bulk studies. This intercalation is found to be reversible via post-deposition rinsing. Furthermore, this work demonstrates that cyclic voltammetry-based deposition enables patterned PPy growth on complex surfaces such as boron-doped carbon nanowalls, overcoming surface charge and wetting challenges. These findings expand the applicability of SECCM for 2D conducting polymer micro-/nanofabrication on both flat and structurally complex substrates.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01781"},"PeriodicalIF":9.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666553","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}
Mingwei Yang, Junrui Tan, Eun-Seong Kim, Longfei Tan, Qiong Wu, Guizhi Zhu, Changhui Fu, Nam-Young Kim, Xiangling Ren, Xianwei Meng
3D printing via direct ink writing (DIW) enables the precise fabrication of macroscale architectures for high-performance electromagnetic wave absorption elastomers (EMWAEs). However, achieving inks that combine excellent printability with superior electromagnetic and mechanical properties remains challenging. Here, a scalable fabrication strategy employing MXene@modified-RGO@SiO2 microspheres synthesized through continuous spheroidization is presented. The incorporation of SiO2 nanoparticles on the microsphere surface preserves the spherical morphology, enhances dispersion within the silicone elastomer matrix, and optimizes rheological behavior for stable DIW extrusion. Guided by electromagnetic simulations, three-layer gradient-porous structures is designed and printed that maximize interfacial polarization and multiple scattering effects. The resulting elastomers exhibit a minimum reflection loss (RLmin) of -44 dB and a maximum effective absorption bandwidth of 7.2 GHz at a thickness of only 3 mm. In addition to their outstanding electromagnetic performance, the printed materials demonstrate improved thermal conductivity and tensile strength, offering a multifunctional platform suitable for flexible and wearable electronic devices. This approach provides a simple, effective, and customizable route for integrating advanced fillers into 3D-printable elastomers, paving the way for next-generation EMWAEs with tunable architectures, broad bandwidth absorption, and mechanical robustness.
{"title":"3D-Printed Gradient-Porous MXene@mRGO@SiO<sub>2</sub> Microspheres/SiC Hybrid Elastomer for Broadband Electromagnetic Wave Absorption.","authors":"Mingwei Yang, Junrui Tan, Eun-Seong Kim, Longfei Tan, Qiong Wu, Guizhi Zhu, Changhui Fu, Nam-Young Kim, Xiangling Ren, Xianwei Meng","doi":"10.1002/smtd.202501581","DOIUrl":"https://doi.org/10.1002/smtd.202501581","url":null,"abstract":"<p><p>3D printing via direct ink writing (DIW) enables the precise fabrication of macroscale architectures for high-performance electromagnetic wave absorption elastomers (EMWAEs). However, achieving inks that combine excellent printability with superior electromagnetic and mechanical properties remains challenging. Here, a scalable fabrication strategy employing MXene@modified-RGO@SiO<sub>2</sub> microspheres synthesized through continuous spheroidization is presented. The incorporation of SiO<sub>2</sub> nanoparticles on the microsphere surface preserves the spherical morphology, enhances dispersion within the silicone elastomer matrix, and optimizes rheological behavior for stable DIW extrusion. Guided by electromagnetic simulations, three-layer gradient-porous structures is designed and printed that maximize interfacial polarization and multiple scattering effects. The resulting elastomers exhibit a minimum reflection loss (RL<sub>min</sub>) of -44 dB and a maximum effective absorption bandwidth of 7.2 GHz at a thickness of only 3 mm. In addition to their outstanding electromagnetic performance, the printed materials demonstrate improved thermal conductivity and tensile strength, offering a multifunctional platform suitable for flexible and wearable electronic devices. This approach provides a simple, effective, and customizable route for integrating advanced fillers into 3D-printable elastomers, paving the way for next-generation EMWAEs with tunable architectures, broad bandwidth absorption, and mechanical robustness.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01581"},"PeriodicalIF":9.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666582","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}
Nano-lignocellulose exhibits great potential for high-value utilization due to its large specific surface area and excellent dispersibility. However, conventional fabrication methods typically rely on chemical reagents, leading to inevitable environmental concerns. Here, a dry processing method for the fabrication of nano-lignocellulose powder is proposed. A mechanical pulverization device based on electromagnetic acceleration is designed, in which multiple coils are sequentially energized to generate magnetic fields, driving magnetic microparticles into high-speed motion. These high-speed magnetic particles collide with lignocellulose and induce its fragmentation, thus enabling the nanoscale fabrication of lignocellulose. Compared with conventional shear-based mechanical pulverization methods, this electromagnetic approach achieves significantly finer particle sizes. Scanning electron microscopy reveals particle sizes of ≈300-400 nm, while Brunauer-Emmett-Teller analysis indicates a 177.2% increase in specific surface area. The absence of solvents ensures retention of the native chemical components. The magnetic fragmentation does not disrupt the lattice, and the original crystalline structure and thermal stability remain unchanged. Mechanical testing of modified biomass composites demonstrates that tensile strength increases with decreasing lignocellulosic particle size. Incorporation of nano-lignocellulose results in a remarkable 72% enhancement in tensile strength compared to neat polylactic acid.
{"title":"Efficient and Clean Method for Nano-Lignocellulose Powder by Particle Collision With Magnetic Acceleration.","authors":"Zhikang Su, Chao Wang, Yichen Liu, Bing Jiang, Chaohui Yang, Benyou Liu, Shen Wang, Yanhui Li, Chuanwei Zhang","doi":"10.1002/smtd.202501664","DOIUrl":"https://doi.org/10.1002/smtd.202501664","url":null,"abstract":"<p><p>Nano-lignocellulose exhibits great potential for high-value utilization due to its large specific surface area and excellent dispersibility. However, conventional fabrication methods typically rely on chemical reagents, leading to inevitable environmental concerns. Here, a dry processing method for the fabrication of nano-lignocellulose powder is proposed. A mechanical pulverization device based on electromagnetic acceleration is designed, in which multiple coils are sequentially energized to generate magnetic fields, driving magnetic microparticles into high-speed motion. These high-speed magnetic particles collide with lignocellulose and induce its fragmentation, thus enabling the nanoscale fabrication of lignocellulose. Compared with conventional shear-based mechanical pulverization methods, this electromagnetic approach achieves significantly finer particle sizes. Scanning electron microscopy reveals particle sizes of ≈300-400 nm, while Brunauer-Emmett-Teller analysis indicates a 177.2% increase in specific surface area. The absence of solvents ensures retention of the native chemical components. The magnetic fragmentation does not disrupt the lattice, and the original crystalline structure and thermal stability remain unchanged. Mechanical testing of modified biomass composites demonstrates that tensile strength increases with decreasing lignocellulosic particle size. Incorporation of nano-lignocellulose results in a remarkable 72% enhancement in tensile strength compared to neat polylactic acid.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01664"},"PeriodicalIF":9.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666591","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}
Yijing Liu, DaVonne Henry, Taylor Terrones, Alexis J Demirjian, Alexey Suslov, Valery Ortiz Jimenez, Ngoc Thanh Mai Tran, Curt A Richter, Albert F Rigosi, Amy Y Liu, Nikolai G Kalugin, Paola Barbara
Since the discovery of graphene, control of its carrier density via doping or functionalization has been a crucial need. Despite significant progress, precise control of the carrier density for epitaxial graphene on SiC remains a challenge. Multiple cycles of doping and characterization are often required before achieving a desired carrier density. In this work, a new approach is demonstrated to precisely program the doping level in top-gated epitaxial graphene devices that are exposed to nitric acid vapor before the gate deposition. With the help of an applied gate voltage, the modification of carrier concentration introduced by the nitric acid can be reversibly controlled, while the corresponding carrier density at zero gate voltage can be accurately tuned by more than 4 × 1013 cm-2 across the charge neutrality point. This gate-assisted molecular doping enables tuning of the charge neutrality point to the desired gate voltage value and can be stabilized by cooling the sample below 200 K.
{"title":"Gate-Assisted Programmable Molecular Doping of Epitaxial Graphene Devices.","authors":"Yijing Liu, DaVonne Henry, Taylor Terrones, Alexis J Demirjian, Alexey Suslov, Valery Ortiz Jimenez, Ngoc Thanh Mai Tran, Curt A Richter, Albert F Rigosi, Amy Y Liu, Nikolai G Kalugin, Paola Barbara","doi":"10.1002/smtd.202501482","DOIUrl":"https://doi.org/10.1002/smtd.202501482","url":null,"abstract":"<p><p>Since the discovery of graphene, control of its carrier density via doping or functionalization has been a crucial need. Despite significant progress, precise control of the carrier density for epitaxial graphene on SiC remains a challenge. Multiple cycles of doping and characterization are often required before achieving a desired carrier density. In this work, a new approach is demonstrated to precisely program the doping level in top-gated epitaxial graphene devices that are exposed to nitric acid vapor before the gate deposition. With the help of an applied gate voltage, the modification of carrier concentration introduced by the nitric acid can be reversibly controlled, while the corresponding carrier density at zero gate voltage can be accurately tuned by more than 4 × 10<sup>13</sup> cm<sup>-2</sup> across the charge neutrality point. This gate-assisted molecular doping enables tuning of the charge neutrality point to the desired gate voltage value and can be stabilized by cooling the sample below 200 K.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01482"},"PeriodicalIF":9.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666551","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}
Houying Ma, Haotian Hu, Jinfeng Ge, Jintao Zhu, Lin Xie, Wei Song, Jing Li, Hainam Do, Ziyi Ge
Strengthening delocalized singlet exciton (DSE) is an effective strategy to improve open-circuit voltage (Voc) and short-circuit current density (Jsc) in organic solar cells (OSCs); however, practical methods to achieve this are still severely limited. In this work, the novel guest acceptor J-OC is introduced to modulate DSE formation as well as bulk heterojunction morphology within the PM6:BTP-eC9 host system. J-OC's low nucleation barrier enables it to act as a seed crystal, effectively accelerating nucleation and optimizing crystallization kinetics. This process significantly enhances crystallinity and crystal perfection, facilitating DSE formation and contributing to improved Voc. Furthermore, GIWAXS and morphology analyses reveal J-OC's multifunctional role in enhancing component miscibility, optimizing exciton distribution, and promoting a fiber-like morphology. Consequently, ternary devices based on PM6:BTP-eC9:J-OC achieved an outstanding power conversion efficiency (PCE) of 20.02%, with simultaneous increases in Voc, Jsc, and fill factor. This performance surpasses binary devices based on PM6:BTP-eC9 (PCE = 19.08%) and PM6:J-OC (PCE = 17.05%). This work demonstrates the synergistic effects of employing a low-nucleation-barrier guest acceptor in a ternary strategy to concurrently optimize DSE formation and morphology.
{"title":"Synergistic Optimization for Exciton Delocalization and Morphology in Ternary Organic Solar Cells Enabled by a Low-Nucleation-Barrier Guest Acceptor.","authors":"Houying Ma, Haotian Hu, Jinfeng Ge, Jintao Zhu, Lin Xie, Wei Song, Jing Li, Hainam Do, Ziyi Ge","doi":"10.1002/smtd.202501707","DOIUrl":"https://doi.org/10.1002/smtd.202501707","url":null,"abstract":"<p><p>Strengthening delocalized singlet exciton (DSE) is an effective strategy to improve open-circuit voltage (V<sub>oc</sub>) and short-circuit current density (J<sub>sc</sub>) in organic solar cells (OSCs); however, practical methods to achieve this are still severely limited. In this work, the novel guest acceptor J-OC is introduced to modulate DSE formation as well as bulk heterojunction morphology within the PM6:BTP-eC9 host system. J-OC's low nucleation barrier enables it to act as a seed crystal, effectively accelerating nucleation and optimizing crystallization kinetics. This process significantly enhances crystallinity and crystal perfection, facilitating DSE formation and contributing to improved V<sub>oc</sub>. Furthermore, GIWAXS and morphology analyses reveal J-OC's multifunctional role in enhancing component miscibility, optimizing exciton distribution, and promoting a fiber-like morphology. Consequently, ternary devices based on PM6:BTP-eC9:J-OC achieved an outstanding power conversion efficiency (PCE) of 20.02%, with simultaneous increases in V<sub>oc</sub>, J<sub>sc</sub>, and fill factor. This performance surpasses binary devices based on PM6:BTP-eC9 (PCE = 19.08%) and PM6:J-OC (PCE = 17.05%). This work demonstrates the synergistic effects of employing a low-nucleation-barrier guest acceptor in a ternary strategy to concurrently optimize DSE formation and morphology.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01707"},"PeriodicalIF":9.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666563","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}
Understanding and establishing the relationship between the defect and macroscopic characteristics is crucial for materials. It is great challenge for linking atomic-scale defect structures to device performance owing to the difficulty in isolating single-type defects in a material. In this work, single-crystal and twin-structured GaN nanowires are prepared, and the performance of photodetectors based on two types of nanowires differs by two order of magnitude. Through analysis of the microstructure at the atomic scale, it is revealed that this difference in performance is due to the presence of unique disconnection structure in the twin nanowires. The embedded dual stacking faults at the disconnection position will introduce stacking mismatch boundaries in the crystal. Combining density functional theory calculations, it is revealed that the stacking mismatch boundary generates deep defect states in the band structure, which explains the performance degradation caused by the { } twin boundary.
{"title":"Adverse Effects of Stacking Mismatch Boundaries on GaN Optoelectronic Properties.","authors":"Jiaxing Wang, Jingyang Zhang, Qinchi Yue, Rui Zhang, Changhao Wang, Xianlin Qu, Zhiyang Xu, Ruzhi Wang, Kun Zheng","doi":"10.1002/smtd.202502316","DOIUrl":"https://doi.org/10.1002/smtd.202502316","url":null,"abstract":"<p><p>Understanding and establishing the relationship between the defect and macroscopic characteristics is crucial for materials. It is great challenge for linking atomic-scale defect structures to device performance owing to the difficulty in isolating single-type defects in a material. In this work, single-crystal and twin-structured GaN nanowires are prepared, and the performance of photodetectors based on two types of nanowires differs by two order of magnitude. Through analysis of the microstructure at the atomic scale, it is revealed that this difference in performance is due to the presence of unique disconnection structure in the twin nanowires. The embedded dual stacking faults at the disconnection position will introduce stacking mismatch boundaries in the crystal. Combining density functional theory calculations, it is revealed that the stacking mismatch boundary generates deep defect states in the band structure, which explains the performance degradation caused by the { <math> <semantics><mrow><mn>10</mn> <mover><mn>1</mn> <mo>¯</mo></mover> <mn>3</mn></mrow> <annotation>${mathrm{10bar 13}}$</annotation></semantics> </math> } twin boundary.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e02316"},"PeriodicalIF":9.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145659862","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}
Spatial transcriptomics has transformed the understanding of gene regulation by enabling high-resolution mapping of RNA molecules within their native cellular and tissue environments. This is typically accomplished by capturing or imaging RNA in situ, thereby preserving spatial context. Here, an in situ RNA imaging method based on split-probe ligation and rolling circle amplification (RCA) for profiling spatial gene expression is introduced. In this approach, split-probes hybridize to adjacent regions of a target RNA fragment and are then enzymatically ligated to form circular DNA templates, which are subsequently amplified via RCA to boost the signal. It is demonstrated that this method enables robust in situ RNA detection and genotyping in both tissue sections and whole-mount tissue samples. By coupling this technique with in situ sequencing, the spatial expression patterns of 82 genes in the kidneys of healthy and diabetic male and female mice are mapped. This analysis reveals distinct localization of Aqp4 in proximal tubules and principal cells of the collecting ducts, and uncovers sex-specific transcriptomic alterations in diabetic kidneys with spatial resolution.
{"title":"Efficient Spatial Gene Expression Profiling Using Split-Probe Ligation and Rolling Circle Amplification.","authors":"Xueqian Xia, Zhaoxiang Xie, Yu Yang, Yanxiu Liu, Weiyan Ma, Bixuan Zhang, Yueping Huang, Yafang Shi, Hui Lin, Lingyu Zhu, Wenhua Li, Chen Lin, Rongqin Ke","doi":"10.1002/smtd.202501615","DOIUrl":"https://doi.org/10.1002/smtd.202501615","url":null,"abstract":"<p><p>Spatial transcriptomics has transformed the understanding of gene regulation by enabling high-resolution mapping of RNA molecules within their native cellular and tissue environments. This is typically accomplished by capturing or imaging RNA in situ, thereby preserving spatial context. Here, an in situ RNA imaging method based on split-probe ligation and rolling circle amplification (RCA) for profiling spatial gene expression is introduced. In this approach, split-probes hybridize to adjacent regions of a target RNA fragment and are then enzymatically ligated to form circular DNA templates, which are subsequently amplified via RCA to boost the signal. It is demonstrated that this method enables robust in situ RNA detection and genotyping in both tissue sections and whole-mount tissue samples. By coupling this technique with in situ sequencing, the spatial expression patterns of 82 genes in the kidneys of healthy and diabetic male and female mice are mapped. This analysis reveals distinct localization of Aqp4 in proximal tubules and principal cells of the collecting ducts, and uncovers sex-specific transcriptomic alterations in diabetic kidneys with spatial resolution.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01615"},"PeriodicalIF":9.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145659815","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}
Shiyu Liu, Xing Lin, Haijin Ji, Kai Huang, Yao Yu, Lin Liu, Yunhui Huang
The formation of lithium dendrites and dead lithium during deposition/stripping process restricts battery performance especially in wide temperature range. However, due to the lack of real-time detection methods, the intrinsic mechanism of how operational temperature affects the dynamic process on lithium metal anodes is still unclear. Here, an in situ investigation of lithium deposition and dead lithium formation during the first charge-discharge cycle in an ether-based electrolyte system is presented. Both the deposition process and stripping process are found to be temperature dependent. Below 293 K, the lithium deposition is less dense plating and the dead lithium is formed, which contributes to the capacity loss. Above 293 K, the lithium deposition becomes denser, and dead lithium formation is significantly reduced. The capacity loss is primarily driven by the formation of solid electrolyte interphase (SEI) resulting from reactions between lithium and ether-based electrolyte. Further study reveals that the ratio of lithium oligoethoxides on the SEI changes abruptly with temperature above 293 K and thus significantly alters the conductivity and reactivity of SEI, which leads to the abrupt change of the deposition/stripping process. These findings highlight the critical role of temperature in lithium deposition/stripping processes in ether-based anode-free lithium metal batteries.
{"title":"Anomalous Temperature Dependence of Lithium Deposition/Stripping Process in Ether-Based Anode-Free Lithium Metal Batteries.","authors":"Shiyu Liu, Xing Lin, Haijin Ji, Kai Huang, Yao Yu, Lin Liu, Yunhui Huang","doi":"10.1002/smtd.202501911","DOIUrl":"10.1002/smtd.202501911","url":null,"abstract":"<p><p>The formation of lithium dendrites and dead lithium during deposition/stripping process restricts battery performance especially in wide temperature range. However, due to the lack of real-time detection methods, the intrinsic mechanism of how operational temperature affects the dynamic process on lithium metal anodes is still unclear. Here, an in situ investigation of lithium deposition and dead lithium formation during the first charge-discharge cycle in an ether-based electrolyte system is presented. Both the deposition process and stripping process are found to be temperature dependent. Below 293 K, the lithium deposition is less dense plating and the dead lithium is formed, which contributes to the capacity loss. Above 293 K, the lithium deposition becomes denser, and dead lithium formation is significantly reduced. The capacity loss is primarily driven by the formation of solid electrolyte interphase (SEI) resulting from reactions between lithium and ether-based electrolyte. Further study reveals that the ratio of lithium oligoethoxides on the SEI changes abruptly with temperature above 293 K and thus significantly alters the conductivity and reactivity of SEI, which leads to the abrupt change of the deposition/stripping process. These findings highlight the critical role of temperature in lithium deposition/stripping processes in ether-based anode-free lithium metal batteries.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01911"},"PeriodicalIF":9.1,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145646820","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}
Zeao Kang, Jinling Zhong, Carlos M Costa, Senentxu Lanceros-Mendez, Linjuan Zhang, Yao Liu, Jian-Qiang Wang
Solid polymer electrolytes (SPEs) offer flexibility and processability but suffer from low ionic conductivity and inadequate mechanical strength. Here, a facile, solvent-free electron beam (EB) irradiation method is introduced to modify poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI)-based SPEs for lithium metal batteries. At an optimal dose, EB irradiation simultaneously generates polar carbonyl groups and induces a crosslinked network. The carbonyl groups facilitate lithium-ion transport and contribute to forming a robust, Li2O-rich solid electrolyte interphase. Concurrently, the crosslinked architecture enhances mechanical integrity and suppresses the growth of lithium dendrites. As a result, Young's modulus increases from 170 to 921 MPa, ionic conductivity rises from 4.7 × 10-4 to 8.2 × 10-4 S cm-1, the lithium-ion transference number (tLi+) improves from 0.29 to 0.48, and the dielectric constant increases from 6.5 to 16.6. Consequently, Li||Li symmetric cells with modified SPE cycle stably for 2000 h (0.05 mA cm-2), 600 h (0.1 mA cm-2), and 180 h (0.2 mA cm-2), with a critical current density of 1.1 mA cm-2. Li||NCM811 (LiNi0.8Co0.1Mn0.1O2) full cells deliver 83.7% capacity retention after 300 cycles at 1C and superior rate performance. This work demonstrates that EB irradiation is a promising and effective strategy for developing high-performance solid-state lithium metal batteries.
固体聚合物电解质(spe)具有灵活性和加工性,但离子电导率低,机械强度不足。本文介绍了一种简单的、无溶剂的电子束(EB)辐照方法,用于改性锂金属电池用聚(二烯基二甲铵)双(三氟甲烷磺酰)亚胺(PDADMATFSI)基spe。在最佳剂量下,EB辐照同时产生极性羰基并诱导交联网络。羰基促进了锂离子的传输,并有助于形成坚固的富含li20的固体电解质界面。同时,交联结构增强了机械完整性,抑制了锂枝晶的生长。杨氏模量从170增加到921 MPa,离子电导率从4.7 × 10-4提高到8.2 × 10-4 S cm-1,锂离子转移数(tLi +)从0.29提高到0.48,介电常数从6.5提高到16.6。因此,在临界电流密度为1.1 mA cm-2的情况下,经过改性SPE的Li||Li对称电池可稳定循环2000 h (0.05 mA cm-2)、600 h (0.1 mA cm-2)和180 h (0.2 mA cm-2)。Li||NCM811 (LiNi0.8Co0.1Mn0.1O2)全电池在1C下循环300次后具有83.7%的容量保持率和优异的倍率性能。研究结果表明,电子束辐照是开发高性能固态锂金属电池的有效方法。
{"title":"Electron Beam Modification of Solid Polymer Electrolytes for Solid-State Lithium Metal Batteries.","authors":"Zeao Kang, Jinling Zhong, Carlos M Costa, Senentxu Lanceros-Mendez, Linjuan Zhang, Yao Liu, Jian-Qiang Wang","doi":"10.1002/smtd.202501980","DOIUrl":"https://doi.org/10.1002/smtd.202501980","url":null,"abstract":"<p><p>Solid polymer electrolytes (SPEs) offer flexibility and processability but suffer from low ionic conductivity and inadequate mechanical strength. Here, a facile, solvent-free electron beam (EB) irradiation method is introduced to modify poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI)-based SPEs for lithium metal batteries. At an optimal dose, EB irradiation simultaneously generates polar carbonyl groups and induces a crosslinked network. The carbonyl groups facilitate lithium-ion transport and contribute to forming a robust, Li<sub>2</sub>O-rich solid electrolyte interphase. Concurrently, the crosslinked architecture enhances mechanical integrity and suppresses the growth of lithium dendrites. As a result, Young's modulus increases from 170 to 921 MPa, ionic conductivity rises from 4.7 × 10<sup>-4</sup> to 8.2 × 10<sup>-4</sup> S cm<sup>-1</sup>, the lithium-ion transference number (t<sub>Li</sub> <sup>+</sup>) improves from 0.29 to 0.48, and the dielectric constant increases from 6.5 to 16.6. Consequently, Li||Li symmetric cells with modified SPE cycle stably for 2000 h (0.05 mA cm<sup>-2</sup>), 600 h (0.1 mA cm<sup>-2</sup>), and 180 h (0.2 mA cm<sup>-2</sup>), with a critical current density of 1.1 mA cm<sup>-2</sup>. Li||NCM811 (LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>) full cells deliver 83.7% capacity retention after 300 cycles at 1C and superior rate performance. This work demonstrates that EB irradiation is a promising and effective strategy for developing high-performance solid-state lithium metal batteries.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01980"},"PeriodicalIF":9.1,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627197","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}
Molybdenum disulfide (MoS2) has attracted a wide range of research attention due to its distinct electronic structures and the great potential for use in emerging microelectronic and photonic devices. However, the development of MoS2-based micro-electronic/photonic devices lags far behind expectations mainly because of the lack of efficient microfabrication technology. Here, a high-resolution precision photoreduction technology is presented for directly printing MoS2 micropatterns that can be decorated into gold nanoparticle (AuNP)/ MoS2 heterostructure for ultrasensitive surface-enhanced Raman spectroscopy (SERS) sensing. Micropatterns of MoSx nanoparticles are initially grown toward a target size in a light-controlled manner and then transformed into a micropatterned pure MoS2 nanofilm through thermal annealing. Thereafter, size and gap-controlled AuNPs are grown selectively on the surface of MoS2 to form a self-aligned AuNP/MoS2 heterostructure with desired optical properties. Thanks to both electromagnetic and chemical enhancements, the directly printed plasmonic AuNP/ MoS2 substrate can greatly enhance Raman signals to detect crystal violet (CV) and 4-mercaptobenzoic acid (4-MBA) at 10-12 m under the excitation of 785-nm laser. This multiscale-engineered plasmonic AuNP/MoS2 substrate is rapidly printed without relying on expensive and time-consuming nanofabrication processes, offering a new technical approach for future development of MoS2-based micro-devices and sensing platforms.
{"title":"Direct Printing of Micropatterned Plasmonic Au Nanoparticle/MoS<sub>2</sub> Heterostructure for Ultrasensitive Surface-Enhanced Raman Spectroscopy Sensing.","authors":"Huimin Xie, Yangxi Zhang, Yu Bai, Hao Li, Dangyuan Lei, Haitao Huang, A Ping Zhang","doi":"10.1002/smtd.202501968","DOIUrl":"https://doi.org/10.1002/smtd.202501968","url":null,"abstract":"<p><p>Molybdenum disulfide (MoS<sub>2</sub>) has attracted a wide range of research attention due to its distinct electronic structures and the great potential for use in emerging microelectronic and photonic devices. However, the development of MoS<sub>2</sub>-based micro-electronic/photonic devices lags far behind expectations mainly because of the lack of efficient microfabrication technology. Here, a high-resolution precision photoreduction technology is presented for directly printing MoS<sub>2</sub> micropatterns that can be decorated into gold nanoparticle (AuNP)/ MoS<sub>2</sub> heterostructure for ultrasensitive surface-enhanced Raman spectroscopy (SERS) sensing. Micropatterns of MoS<sub>x</sub> nanoparticles are initially grown toward a target size in a light-controlled manner and then transformed into a micropatterned pure MoS<sub>2</sub> nanofilm through thermal annealing. Thereafter, size and gap-controlled AuNPs are grown selectively on the surface of MoS<sub>2</sub> to form a self-aligned AuNP/MoS<sub>2</sub> heterostructure with desired optical properties. Thanks to both electromagnetic and chemical enhancements, the directly printed plasmonic AuNP/ MoS<sub>2</sub> substrate can greatly enhance Raman signals to detect crystal violet (CV) and 4-mercaptobenzoic acid (4-MBA) at 10<sup>-12</sup> m under the excitation of 785-nm laser. This multiscale-engineered plasmonic AuNP/MoS<sub>2</sub> substrate is rapidly printed without relying on expensive and time-consuming nanofabrication processes, offering a new technical approach for future development of MoS<sub>2</sub>-based micro-devices and sensing platforms.</p>","PeriodicalId":229,"journal":{"name":"Small Methods","volume":" ","pages":"e01968"},"PeriodicalIF":9.1,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145627245","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}