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High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces. 通过同时调整双电极/电解质界面实现高能量密度锂镍0.8钴0.1锰0.1O2/磷系统的高安全电解质设计
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-27 DOI: 10.1002/smll.202401204
Siyu Fang, Chengyu Han, Shaojie Zhang, Yu Cao, Kang Ma, Yiming Zhang, Xinpeng Han, Juan Wang, Jie Sun

The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.

对最先进的高能量密度锂离子电池的需求与日俱增。然而,传统全电池系统中电极材料的比容量较低,无法满足要求。富镍层状氧化物阴极(如 Li(Ni0.8Co0.1Mn0.1)O2 (NCM811))的理论比容量高达 200 mAh g-1,但在电极/电解质界面上总是伴随着副反应。磷阳极的理论比容量高达 2596 mAh g-1,但体积膨胀很大(≈300%)。本文报告了一种高度兼容和安全的电解质,即在以磷酸三(2,2,2-三氟乙基)酯(TFEP)为共溶剂的 1 m LiPF6 EC/DMC 中引入一种电化学窗口较窄的添加剂--二氟(草酸)硼酸锂(LiDFOB)。LiDFOB 参与了阴极和阳极侧有机/无机混合电极/电解质界面层的形成。NCM811 阴极表面的副反应和磷阳极的体积膨胀得到了有效缓解。使用这种电解液的 NCM811//RP 全电池在 0.5C 速率下循环 150 次后,容量保持率高达 82%。同时,该电解液还具有不燃性。这项工作凸显了操纵电极/电解质界面层对于设计高能量密度锂离子电池的重要性。
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引用次数: 0
Designing Nanofluidic Channels of Boron Nitride Nanosheets/Aramid Nanofibers/Covalent Organic Frameworks Nanofiltration Membrane for Ultrafast Mass Transport. 设计氮化硼纳米片/芳纶纳米纤维/共价有机框架纳米过滤膜的纳米流体通道,实现超快质量传输。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-27 DOI: 10.1002/smll.202402284
Doudou Ning, Zhaoqing Lu, Li Hua, Xinyi Zhang, Nan Li, Kaiyue Huang, Songfeng E

2D lamellar nanofiltration membrane is considered to be a promising approach for desalinating seawater/brackish water and recycling sewage. However, its practical feasibility is severely constrained by the lack of durability and stability. Herein, a ternary nanofiltration membrane via a mixed-dimensional assembly of 2D boron nitride nanosheets (BNNS) is fabricated, 1D aramid nanofibers (ANF), and 2D covalent organic frameworks (COF). The abundant 2D and 1D nanofluid channels endow the BNNS/ANF/COF membrane with a high flux of 194 L·m‒2·h‒1. By the synergies of the size sieving and Donnan effect, the BNNS/ANF/COF membrane demonstrates high rejection (among 98%) for those dyes whose size exceeds 1.0 nm. Moreover, the BNNS/ANF/COF membrane also exhibits remarkable durability and mechanical stability, which are attributed to the strong adhesion and interactions between BNNS, ANF, and COF, as well as the superior mechanical robustness of ANF. This work provides a novel strategy to develop robust and durable 2D lamellar nanofiltration membranes with high permeance and selectivity simultaneously.

二维层状纳滤膜被认为是淡化海水/咸水和回收污水的一种有前途的方法。然而,由于缺乏耐久性和稳定性,其实际可行性受到严重制约。本文通过二维氮化硼纳米片(BNNS)、一维芳纶纳米纤维(ANF)和二维共价有机框架(COF)的混维组装,制造出一种三元纳滤膜。丰富的二维和一维纳米流体通道使 BNNS/ANF/COF 膜的通量高达 194 L-m-2-h-1。通过尺寸筛分和唐南效应的协同作用,BNNS/ANF/COF 膜对尺寸超过 1.0 nm 的染料具有很高的抑制率(98%)。此外,BNNS/ANF/COF 膜还表现出显著的耐久性和机械稳定性,这归功于 BNNS、ANF 和 COF 之间强大的粘附性和相互作用,以及 ANF 优越的机械坚固性。这项研究为开发同时具有高渗透性和高选择性、坚固耐用的二维层状纳滤膜提供了一种新策略。
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引用次数: 0
Low-Symmetry 2D t-InTe for Polarization-Sensitive UV-Vis-NIR Photodetection. 用于偏振敏感型紫外-可见-近红外光电探测的低对称性二维 t-InTe。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-28 DOI: 10.1002/smll.202400311
Nan Zhou, Ziwei Dang, Haoran Li, Zongdong Sun, Shijie Deng, Junhao Li, Xiaobo Li, Xiaoxia Bai, Yong Xie, Liang Li, Tianyou Zhai

Polarization-sensitive photodetection grounded on low-symmetry 2D materials has immense potential in improving detection accuracy, realizing intelligent detection, and enabling multidimensional visual perception, which has promising application prospects in bio-identification, optical communications, near-infrared imaging, radar, military, and security. However, the majority of the reported polarized photodetection are limited by UV-vis response range and low anisotropic photoresponsivity factor, limiting the achievement of high-performance anisotropic photodetection. Herein, 2D t-InTe crystal is introduced into anisotropic systems and developed to realize broadband-response and high-anisotropy-ratio polarized photodetection. Stemming from its narrow band gap and intrinsic low-symmetry lattice characteristic, 2D t-InTe-based photodetector exhibits a UV-vis-NIR broadband photoresponse and significant photoresponsivity anisotropy behavior, with an exceptional in-plane anisotropic factor of 1.81@808 nm laser, surpassing the performance of most reported 2D counterparts. This work expounds the anisotropic structure-activity relationship of 2D t-InTe crystal, and identifies 2D t-InTe as a prospective candidate for high-performance polarization-sensitive optoelectronics, laying the foundation for future multifunctional device applications.

基于低对称性二维材料的偏振敏感光探测技术在提高探测精度、实现智能探测和多维视觉感知等方面具有巨大潜力,在生物识别、光通信、近红外成像、雷达、军事和安防等领域具有广阔的应用前景。然而,大多数已报道的偏振光探测技术都受限于紫外-可见响应范围和较低的各向异性光致发光系数,限制了高性能各向异性光探测技术的实现。本文将二维 t-InTe 晶体引入各向异性系统,并开发出实现宽带响应和高各向异性比偏振光探测的方法。基于二维 t-InTe 晶体的光探测器具有窄带隙和固有的低对称性晶格特性,可实现紫外-可见-近红外宽带光响应和显著的光致各向异性。这项工作阐述了二维 t-InTe 晶体的各向异性结构-活性关系,并确定二维 t-InTe 是高性能偏振敏感光电子学的潜在候选材料,为未来多功能器件的应用奠定了基础。
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引用次数: 0
CuO Nanozymes Catalyze Cysteine and Glutathione Depletion Induced Ferroptosis and Cuproptosis for Synergistic Tumor Therapy. 氧化铜纳米酶催化半胱氨酸和谷胱甘肽耗竭诱导的铁突变和铜突变,实现肿瘤协同治疗
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-30 DOI: 10.1002/smll.202400326
Jinwei Bai, Xuan Zhang, Zhiwen Zhao, Shihao Sun, Wenyuan Cheng, Hongxiang Yu, Xinyue Chang, Baodui Wang

The latest research identifies that cysteine (Cys) is one of the key factors in tumor proliferation, metastasis, and recurrence. The direct depletion of intracellular Cys shows a profound antitumor effect. However, using nanozymes to efficiently deplete Cys for tumor therapy has not yet attracted widespread attention. Here, a (3-carboxypropyl) triphenylphosphonium bromide-derived hyaluronic acid-modified copper oxide nanorods (denoted as MitCuOHA) are designed with cysteine oxidase-like, glutathione oxidase-like and peroxidase-like activities to realize Cys depletion and further induce cellular ferroptosis and cuproptosis for synergistic tumor therapy. MitCuOHA nanozymes can efficiently catalyze the depletion of Cys and glutathione (GSH), accompanied by the generation of H2O2 and the subsequent conversion into highly active hydroxyl radicals, thereby successfully inducing ferroptosis in cancer cells. Meanwhile, copper ions released by MitCuOHA under tumor microenvironment stimulation directly bind to lipoylated proteins of the tricarboxylic acid cycle, leading to the abnormal aggregation of lipoylated proteins and subsequent loss of iron-sulfur cluster proteins, which ultimately triggers proteotoxic stress and cell cuproptosis. Both in vitro and in vivo results show the drastically enhanced anticancer efficacy of Cys oxidation catalyzed by the MitCuOHA nanozymes, demonstrating the high feasibility of such catalytic Cys depletion-induced synergistic ferroptosis and cuproptosis therapeutic concept.

最新研究发现,半胱氨酸(Cys)是肿瘤增殖、转移和复发的关键因素之一。直接消耗细胞内的 Cys 具有显著的抗肿瘤效果。然而,利用纳米酶有效消耗 Cys 来治疗肿瘤尚未引起广泛关注。本文设计了一种由透明质酸衍生的(3-羧丙基)三苯基溴化膦修饰氧化铜纳米棒(MitCuOHA),该纳米棒具有半胱氨酸氧化酶样、谷胱甘肽氧化酶样和过氧化物酶样活性,可实现Cys消耗,并进一步诱导细胞铁突变和铜突变,从而协同治疗肿瘤。MitCuOHA 纳米酶能有效催化 Cys 和谷胱甘肽(GSH)的耗竭,同时产生 H2O2,并随后转化为高活性的羟自由基,从而成功诱导癌细胞的铁凋亡。同时,在肿瘤微环境刺激下,MitCuOHA 释放的铜离子会直接与三羧酸循环中的脂酰化蛋白结合,导致脂酰化蛋白异常聚集,铁硫簇蛋白随之丢失,最终引发蛋白毒性应激和细胞杯突症。体外和体内研究结果表明,MitCuOHA 纳米酶催化的 Cys 氧化作用显著增强了抗癌疗效,证明了这种催化 Cys 耗竭诱导的铁硫协同和杯突症治疗概念的高度可行性。
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引用次数: 0
Enhanced Ionic Power Generation via Light-Driven Active Ion Transport Across 2D Semiconductor Heterostructures. 通过二维半导体异质结构的光驱动活性离子传输增强离子发电。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-06-03 DOI: 10.1002/smll.202311379
Yuhui Zhang, Lili Wang, Qing Bian, Chengcheng Zhong, Yupeng Chen, Lei Jiang

2D semiconductor heterostructures exhibit broad application prospects. However, regular nanochannels of heterostructures rarely caught the researcher's attention. Herein, a metal-organic framework (i.e., Cu3(HHTP)2) and transition metal dichalcogenides (i.e., MoS2)-based multilayer van der Waals heterostructure (i.e., Cu3(HHTP)2/MoS2) realized band alignment-dominated light-driven ion transport and further light-enhanced ionic energy generation. High-density channels of the heterostructure provide high-speed pathways for ion transmembrane transport. Upon light illumination, a net ionic flow occurs at a symmetric concentration, suggesting a directional cationic transport from Cu3(HHTP)2 to MoS2. This is because Cu3(HHTP)2/MoS2 heterostructures containing type-II band alignment can generate photovoltaic motive force through light-induced efficient charge separation to drive ion transport. After introducing into the ionic power generation system, the maximum power density under illumination can achieve notable improvement under different concentration differences. In addition to the photovoltaic motive force, type-II band alignment and material defect capture-induced surface charge increase also raise ion selectivity and flux, greatly facilitating ionic energy generation. This work demonstrates that 2D semiconductor heterostructures with rational band alignment can not only be a potential platform for optimizing light-enhanced ionic energy harvesting but also provide a new thought for biomimetic iontronic devices.

二维半导体异质结构具有广阔的应用前景。然而,异质结构的规则纳米通道很少引起研究人员的注意。在此,一种基于金属有机框架(即 Cu3(HHTP)2)和过渡金属二卤化物(即 MoS2)的多层范德华异质结构(即 Cu3(HHTP)2/MoS2)实现了带排列主导的光驱动离子传输,并进一步实现了光增强离子能量生成。异质结构的高密度通道为离子跨膜传输提供了高速通道。在光照下,离子以对称的浓度净流动,表明阳离子从 Cu3(HHTP)2 向 MoS2 定向传输。这是因为含有 II 型带排列的 Cu3(HHTP)2/MoS2 异质结构可以通过光诱导的高效电荷分离产生光伏动力,从而驱动离子传输。引入离子发电系统后,在不同的浓度差异下,光照下的最大功率密度都能得到显著提高。除了光生伏打动力外,II型带排列和材料缺陷捕获引起的表面电荷增加也提高了离子选择性和通量,极大地促进了离子能源的产生。这项工作表明,具有合理带排列的二维半导体异质结构不仅可以成为优化光增强离子能量收集的潜在平台,还为仿生物离子电子器件提供了新思路。
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引用次数: 0
Electrolyte Superwetting and Electrode Friendly of Porous Membrane for Better Cycling Stability of Lithium Metal Batteries. 多孔膜的电解液超润湿性和电极友好性提高了锂金属电池的循环稳定性。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-06-07 DOI: 10.1002/smll.202401940
Yunchong Feng, Xuebing Zhu, Tengfei Bian, Zewen Liu, Long Zhao, Jinhao Wang, Jinling He, Yong Zhao

Porous polymer membranes as separator plays important roles in separating cathode and anode, storing electrolytes, and transporting ions in energy storage devices. Here, an effective strategy is reported to prepare an electrolyte superwetting membrane, which shows good Li+ transport rate and uniformity, as well as electrode-friendly properties to afford the reduction and oxidation of electrodes. It thereby improves the cycle stability and safety of Li metal batteries. With the arrayed capillaries technique, a thin layer of polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN) composite is uniformly coated on the surface and pores of polypropylene (PP) membrane with a total thickness of 30 µm. After treating it with n-butyllithium and LiNO3 in turn, a chemically inert membrane with efficient and uniform ion transport is prepared, and the cycle stability of Li||Li symmetric cells is up to 1500 h, 4 times higher than that of PP membrane. Moreover, the Li||LiFePO4 with as-prepared membranes achieve a higher capacity retention rate of 92% after 190 cycles at a current density of 3.6 mA cm-2 and a capacity of 3.6 mAh cm-2, and the Li||NCM721 batteries achieve a capacity retention rate of 71% after 600 cycles at a current density of 1.8 mA cm-2.

多孔聚合物膜作为隔膜在储能设备中的阴阳极分离、电解质存储和离子传输方面发挥着重要作用。本文报告了一种制备电解质超湿润膜的有效策略,该膜具有良好的锂+传输速率和均匀性,以及对电极友好的特性,可承受电极的还原和氧化。从而提高了锂金属电池的循环稳定性和安全性。利用阵列毛细管技术,在聚丙烯(PP)膜的表面和孔隙上均匀涂覆一层薄薄的聚偏二氟乙烯(PVDF)和聚丙烯腈(PAN)复合材料,总厚度为 30 µm。在依次用正丁锂和 LiNO3 对其进行处理后,制备出了具有高效、均匀离子传输的化学惰性膜,锂||锂对称电池的循环稳定性高达 1500 h,是 PP 膜的 4 倍。此外,在电流密度为3.6 mA cm-2、容量为3.6 mAh cm-2的条件下,使用制备的膜的Li||LiFePO4电池在循环190次后的容量保持率达到92%,而Li||NCM721电池在电流密度为1.8 mA cm-2、循环600次后的容量保持率达到71%。
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引用次数: 0
[n]Cycloparaphenylenes as Compatible Fluorophores for Melt Electrowriting. 作为熔融电泳兼容荧光团的[n]环联苯。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-06-06 DOI: 10.1002/smll.202400882
Patrick C Hall, Harrison W Reid, Ievgenii Liashenko, Biranche Tandon, Kelly L O'Neill, Naomi C Paxton, Gabriella C J Lindberg, Ramesh Jasti, Paul D Dalton

Fluorescent probes are an indispensable tool in the realm of bioimaging technologies, providing valuable insights into the assessment of biomaterial integrity and structural properties. However, incorporating fluorophores into scaffolds made from melt electrowriting (MEW) poses a challenge due to the sustained, elevated temperatures that this processing technique requires. In this context, [n]cycloparaphenylenes ([n]CPPs) serve as excellent fluorophores for MEW processing with the additional benefit of customizable emissions profiles with the same excitation wavelength. Three fluorescent blends are used with distinct [n]CPPs with emission wavelengths of either 466, 494, or 533 nm, identifying 0.01 wt% as the preferred concentration. It is discovered that [n]CPPs disperse well within poly(ε-caprolactone) (PCL) and maintain their fluorescence even after a week of continuous heating at 80 °C. The [n]CPP-PCL blends show no cytotoxicity and support counterstaining with commonly used DAPI (Ex/Em: 359 nm/457 nm), rhodamine- (Ex/Em: 542/565 nm), and fluorescein-tagged (Ex/Em: 490/515 nm) phalloidin stains. Using different color [n]CPP-PCL blends, different MEW fibers are sequentially deposited into a semi-woven scaffold and onto a solution electrospun membrane composed of [8]CPP-PCL as a contrasting substrate for the [10]CPP-PCL MEW fibers. In general, [n]CPPs are potent fluorophores for MEW, providing new imaging options for this technology.

荧光探针是生物成像技术领域不可或缺的工具,为评估生物材料的完整性和结构特性提供了宝贵的见解。然而,由于熔融电泳(MEW)加工技术需要持续的高温,因此将荧光探针加入到这种加工技术制成的支架中是一项挑战。在这种情况下,[n]环二苯基丙烯([n]CPPs)是用于 MEW 加工的优秀荧光团,其额外优点是在相同激发波长下可定制发射曲线。我们使用了三种不同[n]CPP 的荧光混合物,其发射波长分别为 466、494 或 533 nm,并确定 0.01 wt% 为首选浓度。研究发现,[n]CPP 在聚(ε-己内酯)(PCL)中分散良好,即使在 80 °C 下持续加热一周后仍能保持荧光。n]CPP-PCL混合物无细胞毒性,支持常用的DAPI(波长:359 nm/457 nm)、罗丹明(波长:542/565 nm)和荧光素标记(波长:490/515 nm)类球蛋白染色。使用不同颜色的[n]CPP-PCL 混合物,将不同的 MEW 纤维依次沉积到半编织支架和由[8]CPP-PCL 组成的溶液电纺膜上,作为[10]CPP-PCL MEW 纤维的对比基底。总体而言,[n]CPP 是用于 MEW 的强效荧光团,为该技术提供了新的成像选择。
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引用次数: 0
Harmonic Imaging of Stem Cells in Whole Blood at GHz Pixel Rate. 以 GHz 像素速率对全血中的干细胞进行谐波成像。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-06-11 DOI: 10.1002/smll.202401472
Sebastian Karpf, Nina Glöckner Burmeister, Laurence Dubreil, Shayantani Ghosh, Reka Hollandi, Julien Pichon, Isabelle Leroux, Alessandra Henkel, Valerie Lutz, Jonas Jurkevičius, Alexandra Latshaw, Vasyl Kilin, Tonio Kutscher, Moritz Wiggert, Oscar Saavedra-Villanueva, Alfred Vogel, Robert A Huber, Peter Horvath, Karl Rouger, Luigi Bonacina

The pre-clinical validation of cell therapies requires monitoring the biodistribution of transplanted cells in tissues of host organisms. Real-time detection of these cells in the circulatory system and identification of their aggregation state is a crucial piece of information, but necessitates deep penetration and fast imaging with high selectivity, subcellular resolution, and high throughput. In this study, multiphoton-based in-flow detection of human stem cells in whole, unfiltered blood is demonstrated in a microfluidic channel. The approach relies on a multiphoton microscope with diffractive scanning in the direction perpendicular to the flow via a rapidly wavelength-swept laser. Stem cells are labeled with metal oxide harmonic nanoparticles. Thanks to their strong and quasi-instantaneous second harmonic generation (SHG), an imaging rate in excess of 10 000 frames per second is achieved with pixel dwell times of 1 ns, a duration shorter than typical fluorescence lifetimes yet compatible with SHG. Through automated cell identification and segmentation, morphological features of each individual detected event are extracted and cell aggregates are distinguished from isolated cells. This combination of high-speed multiphoton microscopy and high-sensitivity SHG nanoparticle labeling in turbid media promises the detection of rare cells in the bloodstream for assessing novel cell-based therapies.

细胞疗法的临床前验证需要监测移植细胞在宿主生物组织中的生物分布。在循环系统中实时检测这些细胞并识别其聚集状态是一项关键信息,但需要具有高选择性、亚细胞分辨率和高通量的深度穿透和快速成像。本研究在微流体通道中展示了基于多光子的全血、未过滤血液中人类干细胞的流动检测。该方法依赖于多光子显微镜,通过快速波长扫描激光器在垂直于血流的方向上进行衍射扫描。干细胞被标记为金属氧化物谐波纳米粒子。由于其强大的准瞬时二次谐波发生(SHG),成像速度超过每秒 10,000 帧,像素停留时间为 1 毫微秒,比典型的荧光寿命短,但与 SHG 兼容。通过自动细胞识别和分割,可提取每个检测事件的形态特征,并将细胞聚集与孤立细胞区分开来。这种在浑浊介质中将高速多光子显微镜和高灵敏度 SHG 纳米粒子标记相结合的方法有望检测血液中的稀有细胞,从而评估基于细胞的新型疗法。
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引用次数: 0
A Slightly Expanded Graphite Anode with High Capacity Enabled By Stable Lithium-Ion/Metal Hybrid Storage. 通过稳定的锂离子/金属混合存储实现高容量的轻微膨胀石墨负极。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-28 DOI: 10.1002/smll.202403057
Tong Li, Yun Cao, Qiuchen Song, Linkai Peng, Xianying Qin, Wei Lv, Feiyu Kang

Integrating lithium-ion and metal storage mechanisms to improve the capacity of graphite anode holds the potential to boost the energy density of lithium-ion batteries. However, this approach, typically plating lithium metal onto traditional graphite anodes, faces challenges of safety risks of severe lithium dendrite growth and short circuits due to restricted lithium metal accommodation space and unstable lithium plating in commercial carbonate electrolytes. Herein, a slightly expanded spherical graphite anode is developed with a precisely adjustable expanded structure to accommodate metallic lithium, achieving a well-balanced state of high capacity and stable lithium-ion/metal storage in commercial carbonate electrolytes. This structure also enables fast kinetics of both Li intercalation/de-intercalation and plating/stripping. With a total anode capacity of 1.5 times higher (558 mAh g-1) than graphite, the full cell coupled with a high-loading LiNi0.8Co0.1Mn0.1O2 cathode (13 mg cm-2) under a low N/P ratio (≈1.15) achieves long-term cycling stability (75% of capacity after 200 cycles, in contrast to the fast battery failure after 50 cycles with spherical graphite anode). Furthermore, the capacity of the full cell also reaches a low capacity decay rate of 0.05% per cycle at 0.2 C under the low temperature of -20 °C.

整合锂离子和金属存储机制以提高石墨负极的容量,有望提升锂离子电池的能量密度。然而,这种方法通常是在传统石墨负极上电镀锂金属,由于锂金属容纳空间受限以及在商用碳酸盐电解液中电镀锂不稳定,这种方法面临着严重的锂枝晶生长和短路的安全风险挑战。在此,我们开发了一种略微膨胀的球形石墨负极,其膨胀结构可精确调节,以容纳金属锂,从而在商用碳酸盐电解液中实现高容量和稳定的锂离子/金属存储的平衡状态。这种结构还实现了锂插层/脱插层和镀层/剥离的快速动力学。全电池的阳极总容量是石墨的 1.5 倍(558 mAh g-1),在低 N/P 比(≈1.15)条件下与高负载 LiNi0.8Co0.1Mn0.1O2阴极(13 mg cm-2)耦合,实现了长期循环稳定性(200 次循环后容量达到 75%,而球形石墨阳极在 50 次循环后电池就会快速失效)。此外,在零下 20 °C的低温条件下,全电池的容量衰减率也很低,在 0.2 °C时每循环衰减 0.05%。
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引用次数: 0
I Single-Atom Doped P-Rich CoPn Nanocluster@CoP with Enhanced HER. I 具有增强 HER 的单原子掺杂富 P CoPn 纳米簇@CoP。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 Epub Date: 2024-05-30 DOI: 10.1002/smll.202403170
Haipeng Wang, Chao Zhang, Delu Zhang, Lulu Jiang, Yongsheng Gao, Tao Zhuang, Zhiguo Lv

Constructing I single-atom (ISA) doped CoP electrocatalyst for HER is extremely challenging and has not been reported to date. Herein, an ISA doping-phosphatization strategy is proposed to prepare a novel I single-atom doped P-rich CoPn nanocluster@CoP electrocatalyst (ISA-CoPn/CoP) with enhanced HER performance first. ISA-CoPn/CoP shows a low overpotential of only 44 and 81 mV in 0.5 m H2SO4 solution, to drive a current density of 10 and 100 mA cm-2. ISA and P-rich CoPn nanocluster show unique synergies, which can optimize the H adsorption energy and accelerate the kinetics of HER in the CoP system. The intermediate I─H bond vibration peak is directly observed through in situ Raman testing, demonstrating that ISA doping helps accelerate the HER process. Additionally, the ΔGH of ISA-CoPn/CoP is only 0.05 eV by density functional theory (DFT) calculation, which is conducive to H2 evolution.

构建 I 单原子(ISA)掺杂 CoP 的 HER 电催化剂极具挑战性,迄今为止尚未有相关报道。本文提出了一种 ISA 掺杂-磷化策略,首先制备了一种新型的 I 单原子掺杂富 P CoPn 纳米簇@CoP 电催化剂(ISA-CoPn/CoP),其 HER 性能得到了增强。在 0.5 m H2SO4 溶液中,ISA-CoPn/CoP 的过电位仅为 44 mV 和 81 mV,可驱动 10 mA 和 100 mA cm-2 的电流密度。ISA 和富含 P 的 CoPn 纳米团簇显示出独特的协同作用,可以优化 CoP 系统中 H 的吸附能量并加速 HER 的动力学。通过原位拉曼测试可直接观察到中间的 I─H 键振动峰,这表明 ISA 掺杂有助于加速 HER 过程。此外,通过密度泛函理论(DFT)计算,ISA-CoPn/CoP 的 ΔGH 值仅为 0.05 eV,这有利于 H2 的演化。
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引用次数: 0
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