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Two-Photon Microbubble Printing: Asymmetric Assembly for Continuous Laser Writing (Small 18/2026) 双光子微泡打印:用于连续激光书写的非对称组装(小18/2026)
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-25 DOI: 10.1002/smll.73027
Masaharu Aoyama, Shogo Nara, Hiroshi Numata, Kaito Kimura, Sawa Suzuki, Hiroaki Nishiyama
Continuous Laser Writing
连续激光书写
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引用次数: 0
Bimetallic Bismuth-Based Nanoparticles From Pseudo-Tetrahedral Zintl Anions 伪四面体锌离子制备双金属铋基纳米粒子
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-25 DOI: 10.1002/smll.73221
Megan A. Parker, Dirk Hauschild, Ravi Priya, Constantin Wansorra, Ralph Steininger, Benjamin Peerless, Lothar Weinhardt, Clemens Heske, Stefanie Dehnen
While Zintl compounds comprising Bi-based anions of p-block elements have been used as starting materials for larger bismuth-based clusters, their potential to form nanoparticles has not yet been explored. Here, bimetallic nanoparticles are synthesized from the oxidation of bismuth-based pseudo-tetrahedral Zintl anions (InBi3)2−, (Sn2Bi2)2−, (TlBi3)2−, and (Pb2Bi2)2−. The anions rapidly oxidize at ambient conditions to form metallic seeds, with the mild oxidizing agent PVP (polyvinylpyrrolidone), which also serves as a stabilizing agent for nanoparticle growth. Each elemental combination behaves uniquely, resulting in bimetallic nanoparticles of varying forms (i.e., alloyed, core-shell, and Janus-type). The resulting nanoparticles show a relatively narrow size distribution with median diameters of ∼20–25 nm and exhibit ultraviolet (UV) absorption, with spectral features tunable by composition. The morphology and composition were analyzed by scanning transmission electron microscopy (STEM), high-resolution transmission electron microscopy (HRTEM), micro-X-ray fluorescence spectroscopy (µ-XFS), powder X-ray diffraction (PXRD), synchrotron-based hard and soft X-ray photoelectron spectroscopy (HAXPES and PES), and attenuated total reflectance—Fourier transform infrared spectroscopy (ATR-FTIR). This approach demonstrates that binary Zintl anions can serve as versatile molecular precursors for designing heterometallic nanoparticles with controlled composition, morphology, and optical properties.
虽然含有铋基阴离子的p-嵌段元素的Zintl化合物已被用作更大的铋基簇的起始材料,但它们形成纳米颗粒的潜力尚未被探索。本文通过氧化铋基伪四面体锌离子(InBi3)2−、(Sn2Bi2)2−、(TlBi3)2−和(Pb2Bi2)2−合成了双金属纳米颗粒。阴离子在环境条件下迅速氧化形成金属种子,温和氧化剂PVP(聚乙烯吡咯烷酮)也作为纳米颗粒生长的稳定剂。每一种元素的组合都表现出独特的行为,从而产生不同形式的双金属纳米颗粒(即合金、核壳和janus型)。所得到的纳米颗粒显示出相对狭窄的尺寸分布,中位直径为~ 20-25 nm,具有紫外线(UV)吸收,光谱特征可通过成分调节。采用扫描透射电子显微镜(STEM)、高分辨率透射电子显微镜(HRTEM)、微x射线荧光光谱(µ-XFS)、粉末x射线衍射(PXRD)、基于同步加速器的硬、软x射线光电子能谱(HAXPES和PES)和衰减全反射-傅里叶变换红外光谱(ATR-FTIR)对其形貌和组成进行分析。这种方法表明,二元锌离子可以作为多用途的分子前体,用于设计具有可控组成、形态和光学性质的异金属纳米颗粒。
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引用次数: 0
Nanoscale Ripples at the Surface of SrTiO3 Irradiated by a Broad Low-Energy Ar+ (7 keV) Ion Beam 宽低能Ar+ (7kev)离子束辐照SrTiO3表面的纳米尺度波纹
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-25 DOI: 10.1002/smll.202511071
Mohammad S. Jamal, Isabelle Monnet, Jimmy Rangama, Victor Pierron, Bruno Guillet, Stéphane Guillous, Stéphane Flament, Emmanuel Balanzat, Laurence Méchin, Mamour Sall
The performance of nano-optoelectronic and nano-electronic devices can be significantly enhanced through the integration of well-ordered nanoscale architectures. Ion irradiation has emerged as a powerful bottom-up strategy for fabricating self-organized nanostructures with precise spatial control, offering an effective route to modulate surface morphology and chemistry. We investigated the structural, morphological, and chemical evolution of ripple-like nanostructures formed on single-crystalline SrTiO3 substrates via low-energy Ar+ (7 keV) irradiation at an oblique incidence. Periodic surface ripples were formed within a specific fluence window, where the ripple wavelength remained nearly constant despite a significant increase in surface roughness. Their creation was accompanied by significant structural and chemical changes with argon accumulation, strontium and oxygen depletion. Yet, post-irradiation thermal annealing restored the material crystallinity while preserving the ripple morphology. These findings highlight the potential of ion-beam engineering for creating functional oxide templates with adjustable chemical and structural properties.
通过整合有序的纳米结构,可以显著提高纳米光电和纳米电子器件的性能。离子辐照已经成为一种强大的自下而上的策略,用于制造具有精确空间控制的自组织纳米结构,提供了调制表面形态和化学的有效途径。我们研究了斜入射低能Ar+ (7 keV)辐照在单晶SrTiO3衬底上形成的波纹状纳米结构的结构、形态和化学演变。周期性的表面波纹在一个特定的通量窗口内形成,尽管表面粗糙度显著增加,但波纹波长几乎保持不变。它们的形成伴随着显著的结构和化学变化,包括氩的积累、锶和氧的消耗。然而,辐照后的热退火在保留波纹形貌的同时恢复了材料的结晶度。这些发现突出了离子束工程在创建具有可调节化学和结构特性的功能性氧化物模板方面的潜力。
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引用次数: 0
Advancements in Rechargeable Zinc-Air Batteries: Strategic Modifications in MnxCoyO4 Bifunctional Catalysts and Air Cathode 可充电锌-空气电池的研究进展:MnxCoyO4双功能催化剂和空气阴极的战略性改进
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-25 DOI: 10.1002/smll.73210
Shraddha M. Rajore, Parasharam M. Shirage
This review critically studies MnxCoyO4-based spinel materials as bifunctional electrocatalysts for rechargeable zinc-air batteries (ZABs). It focuses on the fundamentals and extends comprehensive insights of the key electrochemical characterization techniques for evaluating bifunctional electrocatalyst. The influence of crystal structure and symmetry, particularly the dominance of the cubic MnCo2O4 polymorph on the electrochemical performance, is explored in detail, along with comparisons to underexplored tetragonal and trigonal counter forms. Additionally, various potential synthesis strategies are summarized for tailoring morphology and phase in order to control their catalytic activity. Advanced cathode architectures, such as Janus electrodes and binder-free configurations, are also discussed in relation to their role in enhancing air electrode performance. Furthermore, review discusses the performance-enhancing strategies, like facet engineering, alloying, carbon compositing, and transition metal doping. The review is further supported by the inclusion of the emerging concept of anode-free ZABs. A dedicated section highlights the electrochemical metrics of pristine and composite MnCo2O4-based catalysts, offering valuable insight into structure-performance correlations. This focused investigation through this comprehensive review aims to provide guidance in the rational design of high-performance air cathodes for next-generation ZABs and is believed to direct the future research community working in the field of electrocatalysis and air-based rechargeable batteries.
本文综述了mnxcoyo4基尖晶石材料作为可充电锌空气电池(ZABs)双功能电催化剂的研究进展。它侧重于基础和扩展的关键电化学表征技术的综合见解,以评估双功能电催化剂。详细探讨了晶体结构和对称性的影响,特别是立方MnCo2O4多晶对电化学性能的影响,并与未充分研究的四边形和三角形反晶形式进行了比较。此外,还总结了各种可能的合成策略,以调整其形态和相,以控制其催化活性。先进的阴极结构,如Janus电极和无粘结剂配置,也讨论了它们在提高空气电极性能方面的作用。此外,综述还讨论了提高性能的策略,如表面工程、合金化、碳复合和过渡金属掺杂。纳入新兴的无阳极ZABs概念进一步支持了该综述。专门的部分重点介绍了原始和复合mnco2o4基催化剂的电化学指标,为结构-性能相关性提供了有价值的见解。本研究旨在为下一代ZABs高性能空气阴极的合理设计提供指导,并有望指导未来电催化和空气基可充电电池领域的研究工作。
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引用次数: 0
Interstitial Tungsten Atoms as a Primary Defect in Nonstoichiometric WO3-x 间隙钨原子作为非化学计量WO3-x的主要缺陷
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-25 DOI: 10.1002/smll.202514964
Lujun Zhu, Xinyue Xie, Hu Zhang, Jingwei Li, Manling Sui
Nonstoichiometric tungsten oxides (WO3-x) are foundational to technologies from electrochromic devices to photocatalysis. Conventionally, their functional properties are ascribed almost exclusively to oxygen vacancies. Here, using high-quality single-crystalline WO2.72 and by combining atomic-resolution time-resolved STEM with meV-resolution electron energy-loss spectroscopy and density functional theory, we directly reveal interstitial tungsten atoms (Wi) as a previously overlooked but ubiquitous class of point defects, with a quantified concentration of ∼0.11 Wi per unit cell. These Wi atoms reside within the structural tunnels and exhibit dynamic hopping among three metastable sites. In contrast to the shallow states induced by oxygen vacancies, Wi defects create deep, localized electronic states that pin small polarons and induce a pronounced, quantifiable blue-shift of ∼0.3 eV in the absorption edge, as directly measured by atomically resolved EELS. This discovery establishes interstitial transition-metal atoms as a new paradigm of intrinsic defects in nonstoichiometric oxides, offering powerful levers to engineer their electronic and optical functionalities.
非化学计量氧化钨(WO3-x)是从电致变色器件到光催化技术的基础。传统上,它们的功能特性几乎完全归因于氧空位。在这里,使用高质量的单晶WO2.72,并通过结合原子分辨率时间分辨STEM与mev分辨率电子能量损失光谱和密度泛函理论,我们直接揭示了间隙钨原子(Wi)作为以前被忽视但普遍存在的点缺陷,其定量浓度为每单位电池0.11 Wi。这些Wi原子位于结构隧道内,并在三个亚稳位之间表现出动态跳变。与氧空位引起的浅态相反,Wi缺陷产生了深的、局域的电子态,这些电子态可以钉住小的极化子,并在吸收边引起明显的、可量化的蓝移(~ 0.3 eV),这是通过原子分辨EELS直接测量到的。这一发现确立了间隙过渡金属原子作为非化学计量氧化物固有缺陷的新范式,为设计其电子和光学功能提供了强有力的杠杆。
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引用次数: 0
Interfacial Chemistry-Tailored Silica&Metal-Based Heterostructures: from Rational Design to Antibacterial Applications. 界面化学-定制硅和金属基异质结构:从理性设计到抗菌应用。
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-24 DOI: 10.1002/smll.202600038
Dan Cheng,Yuchao Gu,Chengzhong Yu
The escalating global crisis of antimicrobial resistance urgently demands innovative antimicrobial agents beyond conventional antibiotics. Metal-based nanomaterials, including metal/metal oxide nanoparticles (NPs) and metal-organic frameworks (MOFs), represent a promising class of broad-spectrum antibacterial agents. However, their practical application is often hindered by intrinsic limitations such as aggregation, instability, and cytotoxicity. Integrating them with structurally and chemically tunable silica nanoparticles has been demonstrated as a promising strategy to mitigate the limitations and engineer advanced nanohybrids with synergistic functionalities. This review highlights how tailored interfacial chemistry achieves precise architectural control over silica&metal-based nanohybrids. The controlled nanoarchitecture is essential to fully exploit the structural and functional contributions of silica components to overcome the physiochemical limitations of meta-based material. We then examine the biological performance of these heterostructures mainly in antibacterial fields, including membrane disruption, stimuli-responsive activation, biofilm penetration/eradication, and receptor-mediated active targeting to pathogenic bacteria. Finally, challenges and future research directions are outlined based on our own perspectives, providing a design framework for next-generation antimicrobial nanotherapeutics.
不断升级的全球抗微生物药物耐药性危机迫切需要传统抗生素以外的创新抗微生物药物。金属基纳米材料,包括金属/金属氧化物纳米颗粒(NPs)和金属有机框架(mof),代表了一类有前途的广谱抗菌剂。然而,它们的实际应用往往受到诸如聚集性、不稳定性和细胞毒性等内在限制的阻碍。将它们与结构和化学可调的二氧化硅纳米颗粒相结合已被证明是一种很有前途的策略,可以减轻局限性,并设计出具有协同功能的先进纳米杂化材料。这篇综述强调了量身定制的界面化学如何实现对硅基和金属基纳米杂化物的精确结构控制。控制纳米结构对于充分利用二氧化硅组分的结构和功能贡献来克服元基材料的物理化学限制至关重要。然后,我们主要研究了这些异质结构在抗菌领域的生物学性能,包括膜破坏、刺激反应激活、生物膜渗透/根除以及受体介导的对致病菌的活性靶向。最后,基于我们自己的观点,概述了未来的研究方向和挑战,为下一代抗菌纳米治疗药物的设计提供了一个框架。
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引用次数: 0
Quasi-2D Chiral Perovskite Janus-Structural Nanofiber Film With Tunable Spectrum and Energy-Transfer-Amplified Circularly Polarized Luminescence. 具有可调光谱和能量转移放大圆偏振发光的准二维手性钙钛矿双结构纳米纤维薄膜。
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-24 DOI: 10.1002/smll.202513899
Songbing Zhong,Huihui Wang,Yang Chen,Dongming Song,Lintao Shao,Zhi Wang,Yihuang Chen,Shuang Pan,Xue-Qin Bai
Chiral metal halide perovskites hold great potential as circularly polarized luminescent (CPL) materials owing to their exceptional optoelectronic properties. However, chirality-induced lattice distortions in intrinsically chiral systems often reduce photoluminescence (PL) efficiency, making it challenging to balance chirality and emission performance. In this study, we present a general strategy enabling efficient energy transfer (ET) from chiral quasi-two-dimensional (quasi-2D) perovskite nanosheets to achiral perovskite nanocrystals or dye molecules, achieving extended fluorescence lifetimes and enhanced CPL activity in achiral hosts. We establish a direct correlation between ET efficiency and chiral amplification in quasi-2D chiral perovskite/achiral perovskite composites. The Janus-type heterostructures exhibit remarkable ET efficiency and pronounced chiral amplification, leading to a fourfold increase in the photoluminescence quantum yield of achiral components and a luminescence dissymmetry factor (glum) value of 4.32 × 10-3, representing a 50% enhancement compared to pristine chiral perovskites. This design can be extended to achieve full-spectrum, white-light CPL emission. The optimized Janus composites show excellent environmental stability, highlighting their practical applicability. Overall, this work establishes a versatile platform for developing high-efficiency, spectrally tunable, and integrated CPL light sources, providing new opportunities for advanced chiroptoelectronic applications.
手性金属卤化物钙钛矿由于其优异的光电性能,作为圆极化发光材料具有很大的潜力。然而,在固有手性体系中,手性引起的晶格畸变往往会降低光致发光(PL)效率,这使得平衡手性和发射性能变得很困难。在这项研究中,我们提出了一种通用策略,可以从手性准二维钙钛矿纳米片到非手性钙钛矿纳米晶体或染料分子进行有效的能量转移(ET),从而延长荧光寿命并增强非手性宿主的CPL活性。我们在准二维手性钙钛矿/非手性钙钛矿复合材料中建立了ET效率与手性放大之间的直接关联。janus型异质结构表现出显著的ET效率和明显的手性扩增,导致非手性成分的光致发光量子产率提高了4倍,发光不对称因子(glum)值为4.32 × 10-3,与原始手性钙钛矿相比提高了50%。该设计可以扩展到实现全光谱白光CPL发射。优化后的Janus复合材料具有良好的环境稳定性,突出了其实用性。总的来说,这项工作为开发高效,光谱可调和集成的CPL光源建立了一个多功能平台,为先进的光电应用提供了新的机会。
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引用次数: 0
Robust Bioconjugated Antigens Induce Immune Responses Preventing Malaria Infection and its Transmission. 强效生物偶联抗原诱导免疫反应预防疟疾感染及其传播。
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-24 DOI: 10.1002/smll.202508762
Nivethika Sivakumaran,Yevel Flores-Garcia,Chanel M Naar,Shuxiong Chen,Mili Mehta,Fijs W B van Leeuwen,Abhai Tripathi,Rajagopal Murugan,Meta Roestenberg,Fidel Zavala,Bernd H A Rehm
Malaria remains a major global health challenge, with current vaccines providing only limited reductions in case numbers. This study introduces an innovative approach that utilizes engineered Escherichia coli to bioconjugate and assemble the pre-erythrocytic circumsporozoite protein-derived RTS,S antigen and the sexual-stage Pfs47 subdomain into biopolymer particles (BPs), generating the dual-antigen Pfs47-RTS,S-BP vaccine. Compared to single-antigen BPs, the fused Pfs47-RTS,S-BP formulation shows synergistic enhancement in immunogenicity and protective efficacy. Pfs47‑RTS,S‑BP retains its physical properties and antigenicity after storage at 37°C. Although functional in vivo assessment of these thermostable formulations has not yet been performed, the findings indicate promising thermostability that could help overcome cold‑chain limitations in malaria‑endemic regions. Pfs47-RTS,S-BP induces durable antibody and T cell responses alongside crucial liver-resident memory T cells for frontline defence. Vaccine-induced antibodies efficiently neutralize sporozoites and inhibit parasite transmission. Pfs47-RTS,S-BP generates RTS,S-specific antibody levels 5.3-fold higher than the protective thresholds of the current RTS,S/AS01 vaccine. The Pfs47-RTS,S-BP formulation also achieves 80.4% protection against mosquito bite challenge and 68.15% transmission-reducing activity, demonstrating strong potential as a robust, dual-stage malaria vaccine candidate. Overall, this work underscores the potential of Pfs47‑RTS, S‑BP to overcome key limitations of current vaccines and to substantially advance global malaria control efforts.
疟疾仍然是一项重大的全球卫生挑战,目前的疫苗只能有限地减少病例数。本研究介绍了一种创新的方法,利用工程大肠杆菌将红细胞前环孢子子蛋白衍生的RTS,S抗原和性期Pfs47亚结构域生物偶联并组装成生物聚合物颗粒(bp),产生双抗原Pfs47-RTS,S- bp疫苗。与单抗原bp相比,融合Pfs47-RTS、S-BP制剂在免疫原性和保护功效方面具有协同增强作用。Pfs47 - RTS,S - BP在37°C保存后保持其物理特性和抗原性。尽管尚未对这些热稳定性配方进行体内功能评估,但研究结果表明,有希望的热稳定性可以帮助克服疟疾流行地区的冷链限制。Pfs47-RTS,S-BP诱导持久抗体和T细胞反应,以及关键的肝驻留记忆T细胞,用于前线防御。疫苗诱导的抗体有效地中和孢子子并抑制寄生虫传播。Pfs47-RTS,S- bp产生的RTS,S特异性抗体水平比当前RTS,S/AS01疫苗的保护阈值高5.3倍。Pfs47-RTS,S-BP制剂对蚊虫叮咬的保护率达到80.4%,减少传播的活性达到68.15%,显示出作为一种强大的双期疟疾候选疫苗的强大潜力。总的来说,这项工作强调了Pfs47 - RTS, S - BP在克服当前疫苗的主要局限性和大幅推进全球疟疾控制工作方面的潜力。
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引用次数: 0
Integrating Experiments and Simulations to Uncover Size-Dependent Bioactivity in Cellular Nanodiscs. 整合实验和模拟揭示细胞纳米盘的大小依赖的生物活性。
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-24 DOI: 10.1002/smll.202514624
Kailin Feng,Yun Chen,Jiayuan Alex Zhang,Zhidong Zhou,Lei Sun,Wei-Ting Shen,Weiwei Gao,Kesong Yang,Liangfang Zhang
Cell membrane-derived nanodiscs or cellular nanodiscs (CNDs) integrate the structural fidelity of biological membranes with the tunability of synthetic nanomaterials, creating a versatile platform for therapeutic and diagnostic applications. Despite growing interest, the relationship between CND size and biological function has not been systematically defined. In this work, we combine experimental and computational approaches to elucidate how CND size governs its performance. Using red blood cell (RBC)-derived CNDs generated with styrene-maleic anhydride copolymers of varying styrene-to-maleic anhydride ratios, we produced three uniform and highly stable CND formulations with diameters of approximately 71, 26, and 15 nm. Functional studies revealed that smaller CNDs exhibited significantly enhanced antibody binding and faster interaction kinetics. Brownian dynamics simulations attributed these improvements to increased diffusion coefficients and higher particle numbers at reduced sizes. In agreement with these predictions, the smallest CNDs demonstrated the most potent α-toxin neutralization in vitro and provided the greatest survival benefit in a mouse intoxication model. Collectively, these findings demonstrate that precise size control is a key determinant of CND bioactivity and offer design principles for optimizing CND formulations towards optimal biological applications.
细胞膜衍生的纳米片或细胞纳米片(CNDs)将生物膜的结构保真度与合成纳米材料的可调性结合在一起,为治疗和诊断应用创造了一个多功能平台。尽管人们对CND的兴趣日益浓厚,但CND大小与生物学功能之间的关系尚未得到系统的定义。在这项工作中,我们结合实验和计算方法来阐明CND尺寸如何控制其性能。利用不同苯乙烯与马来酸酐比例的苯乙烯-马来酸酐共聚物生成的红细胞源性CND,我们生产了三种均匀且高度稳定的CND配方,直径分别为71、26和15 nm。功能研究表明,较小的CNDs具有显著增强的抗体结合和更快的相互作用动力学。布朗动力学模拟将这些改进归因于扩散系数的增加和尺寸减小时颗粒数量的增加。与这些预测一致,最小的CNDs在体外表现出最有效的α-毒素中和作用,并在小鼠中毒模型中提供了最大的生存益处。总的来说,这些发现表明,精确的尺寸控制是CND生物活性的关键决定因素,并为优化CND配方提供了设计原则,以实现最佳的生物应用。
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引用次数: 0
Zn-Ion Storage in an Anode-Protected High-Performance Aqueous Organic Zinc Ion Battery. 阳极保护高性能水性有机锌离子电池中的锌离子存储。
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-03-24 DOI: 10.1002/smll.202600014
Subhankar Mandal,Priti Singh,Dipen Biswakarma,Rekha Kumari,Martin A Karlsen,Martin Etter,Mudit Dixit,Aninda J Bhattacharyya
In this work, we discuss the complexities of Zn2+-ion storage in an organic stacked layered naphthalenediimide (NDI) via systematic experimentation and theoretical calculations. Apart from the possibility of insertion/deinsertion, NDI also provides redox-active docking motifs for Zn2+-ions. Additionally, the anode-associated challenges are mitigated using zinc phthalocyanine (ZnPc) as an organometallic protective layer. Despite achieving a high coulombic efficiency (>99%) at high cycle numbers, capacity degradation is observed during long-term cycling. The observed capacity fade is attributed to the underlying NDI's transformation from a hexagonal to a flower-like morphology. This structural evolution is attributed to the co-insertion of Zn2+ and protons from the electrode/electrolyte interface into the bulk cathode via coordination with carbonyl (─CO) and amine (─NH2) groups. Additionally, the capacity fade is attributed to the sluggish kinetics of Zn2+ stripping/plating. The ZnPc protective layer effectively guides Zn2+ deposition along the (002) crystal plane, suppresses side reactions, and enhances both the capacity retention and cycling stability of the battery. Accounting for Zn2+-ion storage in a redox-active organic host through the elucidation of key roles in phase transitions, ion diffusion dynamics, and zinc electrodeposition/dissolution processes provides a deep-dive conceptual framework for designing novel organic Zn2+-ion hosts for practical AZIBs.
在这项工作中,我们通过系统的实验和理论计算,讨论了Zn2+离子在有机堆叠层状萘二亚胺(NDI)中存储的复杂性。除了插入/脱插入的可能性,NDI还为Zn2+离子提供了氧化还原活性的对接基序。此外,使用酞菁锌(ZnPc)作为有机金属保护层可以减轻阳极相关的挑战。尽管在高循环次数下实现了高库仑效率(>99%),但在长期循环过程中观察到容量下降。观测到的容量衰减归因于潜在的NDI从六边形到花状形态的转变。这种结构演变归因于Zn2+和质子从电极/电解质界面通过与羰基(─CO)和胺(─NH2)基团配位进入体阴极。此外,容量衰减是由于Zn2+剥离/镀动力学缓慢所致。ZnPc保护层有效地引导Zn2+沿(002)晶面沉积,抑制副反应,提高电池的容量保持率和循环稳定性。通过阐明在相变、离子扩散动力学和锌电沉积/溶解过程中的关键作用来解释Zn2+离子在氧化还原活性有机宿主中的储存,为设计用于实际azib的新型有机Zn2+离子宿主提供了一个深入的概念框架。
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