Rare Metals最新文献_第4页

Elaborately designed multilayers honeycomb-like MXene/BPQDs hierarchical architecture anode for SIBs with excellent kinetics 精心设计多层蜂窝状MXene/BPQDs分层结构阳极，具有优异的动力学性能

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-13 DOI: 10.1007/s12598-025-03496-4

Jin-Hao Zhang, Li-Su Zhang, Tian-Sheng Mu, Yue Liang, Fei-Li Lai, Xiao-Dong Zhu

Black phosphorus quantum dots (BPQDs) show great promise as anode material for sodium-ion batteries (SIBs) due to their high theoretical capacity and short ion diffusion pathways. However, the challenges of low electronic conductivity and aggregation of BPQDs hinder their performance in SIBs. Loading BPQDs onto MXene nanosheets can address these issues, but the two-dimensional nanosheets may restack into a dense film during the filtration process, limiting reaction kinetics. Here, we report, for the first time, a bionic strategy for multilayer honeycomb-like MXene/BPQDs (MLHM/BPQDs) hierarchical architecture anode for SIBs. MXene nanosheets are arranged to ordered honeycomb layers and interlayer channels through the dual-template method. MXene nanosheets are arranged to ordered honeycomb layers and interlayer channels through the dual-templates method, and then, BPQDs are uniformly self-assembled onto the inwalls of the honeycomb. The unique open hierarchical architecture serves as an excellent substrate for rapid electron transport. Its large specific surface area offers more sites for BPQDs loading, preventing aggregation, and provides abundant channels and space for electrolyte infiltration and BPQDs volume change. The -O terminal groups increased after annealing, and the abundant -O/-F terminal groups on the surface of MXene can effectively enhance the binding energy and diffusion rate of Na⁺. The synergy of structure and surface chemistry accelerates the kinetics for MLHM/BPQDs, delivering a high reversible capacity of 653 mAh g⁻¹ after 500 cycles at 2 A g⁻¹ (94.3% capacity retention), which demonstrates its great potential as a SIBs anode material.

Graphical abstract

黑磷量子点（BPQDs）具有理论容量大、离子扩散路径短等优点，作为钠离子电池的负极材料具有广阔的应用前景。然而，低电子导电性和bpqd聚集的挑战阻碍了它们在sib中的性能。将bpqd加载到MXene纳米片上可以解决这些问题，但在过滤过程中，二维纳米片可能会重新堆叠成致密膜，限制反应动力学。在这里，我们首次报道了一种用于sib的多层蜂窝状MXene/BPQDs （MLHM/BPQDs）分层结构阳极的仿生策略。通过双模板法将MXene纳米片排列成有序的蜂窝层和层间通道。通过双模板方法将MXene纳米片排列成有序的蜂窝层和层间通道，然后将bpqd均匀地自组装到蜂窝内壁上。独特的开放层次结构是快速电子传递的优良衬底。其较大的比表面积为BPQDs的加载提供了更多的位点，防止了BPQDs的聚集，并为电解质的渗透和BPQDs的体积变化提供了丰富的通道和空间。退火后-O端基团增加，MXene表面丰富的-O/-F端基团能有效提高Na+的结合能和扩散速率。结构和表面化学的协同作用加速了MLHM/ bpqd的动力学，在2 a g−1下循环500次后，提供了653 mAh g−1的高可逆容量（94.3%的容量保留率），这表明其作为SIBs阳极材料的巨大潜力。图形抽象

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引用次数: 0

Rare earth bimetallic organic framework-derived lean-zinc anodes for highly reversible zinc-metal batteries 用于高可逆锌金属电池的稀土双金属有机框架衍生贫锌阳极

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-12 DOI: 10.1007/s12598-025-03498-2

Wen-Shuo Zhang, Chao Li, Xiao-Meng Shi, Zhi-Chao Zeng, Ya-Ping Du

Aqueous zinc-metal batteries have many advantages, including high safety, low cost, and environmental friendliness. Nevertheless, the poor cycling stability hinders their practical application. Mitigating the irreversible Zn²⁺ loss at the interface between the electrode and electrolyte, as well as inside the electrode, is an effective strategy to achieve high cycling stability. Herein, a novel lean-zinc anode is proposed, which is carried out by annealing LaZn bimetallic organic framework to form metal oxides and derived carbon. The anode has a low voltage hysteresis and low nucleation overpotential, further achieves high plating/stripping reversibility. The good electrochemical properties are attributed to the highly stable anode, which contains a large layer spacing La₂O₃ with a low lattice mismatch degree to Zn⁰. This anode facilitates rapid ion transport and uniform Zn⁰ deposition at the interface, which helps to alleviate the irreversible Zn²⁺ loss. On this basis, the assembled batteries can maintain excellent stability for over 3000 cycles. This illustrates the promising application of rare-earth-based bimetallic-derived anodes in aqueous zinc-metal batteries.

Graphical abstract

锌金属水电池具有安全性高、成本低、环境友好等优点。然而，较差的循环稳定性阻碍了它们的实际应用。减轻电极与电解液界面以及电极内部不可逆的Zn2+损耗是实现高循环稳定性的有效策略。本文提出了一种新型贫锌阳极，该阳极通过退火锌双金属有机骨架形成金属氧化物和衍生碳。阳极具有低电压滞回和低成核过电位，进一步实现了高镀剥离可逆性。良好的电化学性能归功于高稳定性的阳极，其含有大层间距的La2O3，与Zn0的晶格错配度低。这种阳极有利于离子的快速传递和Zn0在界面的均匀沉积，有助于减轻Zn2+的不可逆损失。在此基础上，组装的电池可以在3000多个循环中保持优异的稳定性。这说明了稀土基双金属衍生阳极在水锌金属电池中的应用前景。图形抽象

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引用次数: 0

The synergy of structural constraints and lattice engineering endows Ba2.80Sr0.20Sc(BO2)9: Eu3+ phosphor with a concentration-free quenching effect and far-red emission 结构约束和晶格工程的协同作用使得Ba2.80Sr0.20Sc(BO2)9: Eu3+荧光粉具有无浓度猝灭效应和远红发射特性

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-11 DOI: 10.1007/s12598-025-03513-6

Xiao-Qing Pei, Li-Na Liu, Chun Li, Hai Lin, Sha-Sha Li, Wei-Ling Yang, Fan-Ming Zeng

Eu³⁺-activated red phosphors are popular for their classic ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) emission characteristics. However, the weak emission of the ⁵D₀ →⁷F₄ transition and the concentration quenching caused by energy migration have become the main obstacles to achieving strong far-red emission. Herein, we report a novel Ba₃Sc_1-x(BO₂)₉: xEu³⁺ phosphor that simultaneously enhances ⁵D₀ → ⁷F₄ emission and suppresses quenching through size confinement and low phonon energy. A Sr²⁺ → Ba²⁺ substitution strategy optimizes luminescence, achieving 1.56-fold intensity enhancement and improved quantum efficiency (IQE: 83% → 92%; EQE: 38% → 40%). The improvement mechanism was revealed through the local coordination distortion of Eu³⁺ and the change of the band gap when Sr and Ba coexist. Structural analysis reveals enhanced thermal stability (423 K: 86% → 97%; 483 K: 78% → 95%) originates from increased lattice rigidity. Abnormal thermal quenching (303–363 K) is white light-emitting diodes (WLEDs) device prepared based on Ba_2.80Sr_0.20Eu(BO₂)₉ phosphor shows a color temperature of 4532 K and a color rendering index of 91.6. This article also explores three applications of plant growth, latent fingerprint visualization, and anti- counterfeiting QR code. This finding provides a reference for further exploring the design of high concentration quenching and efficient far-red emitting phosphors.

Graphical Abstract

Eu3+活化的红色荧光粉因其经典的5D0→7FJ （J = 0,1,2,3,4）发射特性而广受欢迎。然而，5D0→7F4跃迁的弱发射和能量迁移引起的浓度猝灭成为实现强远红发射的主要障碍。在此，我们报道了一种新的Ba3Sc1-x(BO2)9: xEu3+荧光粉，它同时增强5D0→7F4发射并通过尺寸限制和低声子能量抑制猝灭。Sr2+→Ba2+取代策略优化了发光，实现了1.56倍的强度增强和量子效率的提高（IQE: 83%→92%;EQE: 38%→40%）。通过Sr和Ba共存时Eu3+的局部配位畸变和带隙的变化揭示了改善机理。结构分析表明，增强的热稳定性（423 K: 86%→97%;483 K: 78%→95%）源于晶格刚度的增加。基于Ba2.80Sr0.20Eu(BO2)9荧光粉制备的异常热猝灭（303-363 K）白光二极管（wled）器件，其色温为4532 K，显色指数为91.6。本文还探讨了植物生长、潜在指纹可视化和防伪二维码的三种应用。这一发现为进一步探索高浓度猝灭高效远红发光荧光粉的设计提供了参考。图形抽象

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引用次数: 0

Enhanced performance of lithium-sulfurized polyacrylonitrile batteries via multifunctional CoS2/NiS2 heterostructures and intrinsic electric fields 利用多功能CoS2/NiS2异质结构和本征电场增强锂硫化聚丙烯腈电池性能

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-11 DOI: 10.1007/s12598-025-03525-2

Hao Liu, Hai-Hui Liu, Qiang Xu, Xiao-Dong Shao, Xiao Zhang, Shu-Liang Lv, Zhi-Jia Zhang, Chang Ma, Yan-Mei Jin

Lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries are an advanced class of Li–S energy storage systems that effectively mitigate the polysulfide shuttle effect. However, conventional SPAN cathodes experience low active material retention (< 40 wt%) and sluggish electrochemical kinetics, which limit their practical application. To address these challenges, this study introduces a CoS₂/NiS₂@SeSPAN composite nanofiber membrane as a high-performance Li-SPAN cathode. The cathode was synthesized through electrospinning Co/Ni salts with PAN, followed by hydrothermal deposition of Ni-ZIF-67 and SeS_x-assisted thermal treatment to form a CoS₂/NiS₂ heterostructure within the SeSPAN matrix. Experimental validation and density functional theory simulations confirmed that the cathode electrolyte interphase layer effectively encapsulated the active material, extending the solid-state reaction pathway. This hierarchical porous architecture enabled a high active material loading of 59 wt%, which considerably exceeds that of conventional SPAN-based cathodes. The three-dimensional interconnected fiber network maximized the exposure of the CoS₂/NiS₂ heterojunction, while the metal sulfides increased the conductivity to facilitate efficient electron and ion transport. The intrinsic electric field within the CoS₂/NiS₂ heterostructure further enhanced polysulfide adsorption and catalytic conversion, accelerating the electrochemical kinetics. As a result, the CoS₂/NiS₂@SeSPAN cathode had an initial discharge capacity of 678 mAh g⁻¹ at 0.2C, maintaining 634 mAh g⁻¹ at 0.5C. Remarkably, the battery maintained 98.2% of its capacity after 800 cycles, highlighting its outstanding long-term cycling stability. The substantial potential of CoS₂/NiS₂@SeSPAN for high-performance Li-SPAN batteries and the critical role of heterostructure engineering in next-generation energy storage technologies are highlighted in this study.

Graphical abstract

锂硫化聚丙烯腈（Li-SPAN）电池是一种先进的锂硫电池储能系统，可有效缓解多硫化物穿梭效应。然而，传统的SPAN阴极具有活性物质保留率低（40% wt%）和电化学动力学缓慢的特点，这限制了其实际应用。为了解决这些挑战，本研究引入了CoS2/NiS2@SeSPAN复合纳米纤维膜作为高性能Li-SPAN阴极。采用PAN静电纺丝Co/Ni盐合成阴极，再通过水热沉积Ni- zif -67和sesx辅助热处理，在SeSPAN基体内形成CoS2/NiS2异质结构。实验验证和密度泛函理论模拟证实，阴极电解质间相层有效封装了活性物质，延长了固态反应途径。这种分层多孔结构使活性材料负载高达59%，大大超过了传统的基于span的阴极。三维互连光纤网络最大限度地暴露了CoS2/NiS2异质结，而金属硫化物增加了电导率，促进了电子和离子的有效传递。CoS2/NiS2异质结构内的本征电场进一步增强了多硫化物的吸附和催化转化，加速了电化学动力学。结果表明，CoS2/NiS2@SeSPAN阴极在0.2C时的初始放电容量为678 mAh g−1，在0.5C时保持634 mAh g−1。值得注意的是，电池在800次循环后保持了98.2%的容量，突出了其出色的长期循环稳定性。本研究强调了CoS2/NiS2@SeSPAN在高性能Li-SPAN电池中的巨大潜力，以及异质结构工程在下一代储能技术中的关键作用。图形抽象

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引用次数: 0

Synchronous dual-modification strategy of K+ intercalation and CrOx coating enabling durable zinc-ion storage in vanadium oxide K+插层和CrOx涂层同步双改性策略，使锌离子在氧化钒中持久储存

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-11 DOI: 10.1007/s12598-025-03438-0

Xinliang Zhou, Wenjing He, Menghe Jia, Mengqi Ren, Xingrui Li, Ang Cao, Dong-sheng Li, Shuang Li, Naiteng Wu, Xianming Liu

The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries (AZIBs). Although the conventional ion doping method mitigates the intrinsically sluggish kinetics, it exacerbates the erosion of Zn²⁺/H⁺ and free water within the lattice structure, leading to inferior structural stability and capacity fading. Herein, a synchronous dual-modification strategy is introduced to improve the electrochemical performance of the V₆O₁₃ cathode through an ingenious hydrolysis process involving K₂Cr₂O₇. Experimental and calculated results demonstrate that the coating layer formed by chromium oxide supports the structural firmness and strengthens the interfacial chemistry, based on increased electrochemical activity by K⁺ intercalation. Consequently, the optimized sample delivers a capacity of 418 mAh g⁻¹ at 0.1 A g⁻¹, and excellent cyclic stability of 205 mAh g⁻¹ after 6000 cycles at 10 A g⁻¹. It is fully charged at a small current of 0.5 A g⁻¹ to maintain a reversible capacity of 346 mAh g⁻¹ after 72 h in an open circuit state, and there is no obvious capacity decay, highlighting the crucial protective effect of the inactive coating layer. This work presents a straightforward and reliable approach to effectively harmonize the relationship between activity and structural stability for advanced AZIBs cathode.

Graphical abstract

不同的价态和空间结构赋予了钒氧化物在水锌离子电池领域的巨大潜力。虽然传统的离子掺杂方法减轻了内在缓慢的动力学，但它加剧了晶格结构内Zn2+/H+和自由水的侵蚀，导致结构稳定性差和容量衰退。本文提出了一种同步双改性策略，通过巧妙的K2Cr2O7水解工艺来提高V6O13阴极的电化学性能。实验和计算结果表明，通过K+的插入，氧化铬形成的涂层支持了结构的坚固性，增强了界面化学性质。因此，优化后的样品在0.1 a g−1下提供418 mAh g−1的容量，在10 a g−1下循环6000次后提供205 mAh g−1的优异循环稳定性。在0.5 a g−1的小电流下充满电，在开路状态下72 h后仍保持346 mAh g−1的可逆容量，并且没有明显的容量衰减，突出了非活性涂层的关键保护作用。本文提出了一种简单可靠的方法来有效地协调先进azib阴极的活性与结构稳定性之间的关系。图形抽象

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引用次数: 0

Confronting pressure and humidity limitations in gold nanoparticle sensors array for enhancing electronic nose technology in real-world applications 面对压力和湿度的限制，金纳米颗粒传感器阵列增强电子鼻技术在现实世界中的应用

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-08 DOI: 10.1007/s12598-025-03521-6

Xue Jiang, Dan-Yao Qu, Jun-Nan Zhang, Viki Kloper, Ke-Fan Zhang, Guang-Jian Zhang, Lei Wang, Ming-Hu Pan, Quan-Min Guo, Li Chen, Wei-Tian Huang, Jian-Zhi Gao, Hossam Haick, Wei-Wei Wu

The field of disease smelling diagnosis has experienced a major breakthrough with the development of the electronic nose (E-nose) that utilizes thiol-capped gold nanoparticles (GNPs). This study focuses on overcoming the challenges of sensors to detect VOCs stably confounding with interferents of humidity and pressure, and clarifying their essential mechanism. An innovative and straightforward method for synthesizing GNPs and modifying their surface has been developed. This unique approach deviates from the conventional Brust method by completely removing any traces of tetraoctylammonium bromide (TOAB), ensuring reproducibility and simplicity of use. This modification enhances the sensor’s responsiveness to both polar and non-polar VOCs, as well as strengthen selectivity and anti-interferant capabilities. The mechanism of generating sensing cross-talk from TOAB residue is proposed through rigorous sensing experiments, X-ray photoelectron spectroscopy (XPS) results, and theoretical analysis. Thus, this study enhances the responsiveness of the sensor to both polar and non-polar VOCs, while also strengthening its selectivity and anti-interferent capabilities. This could potentially revolutionize the practical applications of E-nose in smelling diagnosis.

Graphical abstract

随着利用硫醇包覆金纳米粒子（GNPs）的电子鼻（E-nose）的发展，疾病嗅觉诊断领域取得了重大突破。本研究的重点是克服传感器在湿度和压力干扰下稳定检测VOCs的挑战，并阐明其基本机制。本文提出了一种新颖而直接的合成GNPs及其表面修饰方法。这种独特的方法与传统的Brust方法不同，它完全去除了四辛基溴化铵（TOAB）的任何痕迹，确保了可重复性和简单性。该修饰提高了传感器对极性和非极性VOCs的响应性，增强了选择性和抗干扰能力。通过严格的传感实验、x射线光电子能谱（XPS）结果和理论分析，提出了TOAB残基产生传感串扰的机理。因此，本研究增强了传感器对极性和非极性VOCs的响应性，同时也增强了其选择性和抗干扰能力。这可能会彻底改变电子鼻在嗅觉诊断中的实际应用。图形抽象

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引用次数: 0

Synergistic effect of piezoelectricity and LSPR effect to boost efficient photocatalytic CO2RR 压电效应和LSPR效应协同提高光催化CO2RR效率

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-08 DOI: 10.1007/s12598-025-03479-5

Lu Liu, Qi An, Hai-Ye Zhu, Lei Qiu, Qing Liu, Hong Guo

The application of a piezoelectric field based on photocatalytic CO₂ reduction reaction is a new strategy to overcome the rapid charge recombination. Herein, NaNbO₃–Ag–AgBr heterojunction synergizing piezoelectric polarization and the localized surface plasmon resonance (LSPR) effect is designed. Under the simultaneous excitation of light and ultrasound, piezoelectric field drives the separation of directional charge, and Ag nanoparticles enhance the absorption of visible light and the injection of hot electrons. Meanwhile, the mechanism of carrier transport in heterojunction under the synergistic action of piezoelectric field and LSPR effect is also studied. The research shows the CO yield of NaNbO₃-Ag-AgBr is 153.21 µmol g⁻¹ and nearly 17 times higher than that of NaNbO₃. In situ infrared spectroscopy, piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) results show that piezoelectric polarization reduces the Schottky barrier at the interface, promotes the transfer of hot electrons and inhibits the rapid bulk phase charge recombination. Thus, the piezoelectric photocatalytic system provides more profound insights for photocatalytic CO₂RR.

Graphical abstract

基于光催化CO2还原反应的压电场的应用是克服快速电荷复合的新策略。本文设计了NaNbO3-Ag-AgBr异质结协同压电极化和局域表面等离子体共振（LSPR）效应。在光和超声的同时激发下，压电场驱动定向电荷的分离，Ag纳米粒子增强了对可见光的吸收和热电子的注入。同时，研究了压电场和LSPR效应协同作用下异质结中载流子输运的机理。研究表明，NaNbO3- ag - agbr的CO产率为153.21µmol g−1，是NaNbO3的近17倍。原位红外光谱、压电响应力显微镜（PFM）和开尔文探针力显微镜（KPFM）结果表明，压电极化降低了界面处的肖特基势垒，促进了热电子的转移，抑制了体相电荷的快速复合。因此，压电光催化系统为光催化CO2RR提供了更深刻的见解。图形抽象

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引用次数: 0

Ultrathin graphite-encapsulated Y2Co17 nanostructures with good structural stability and switchable microwave absorption 超薄石墨封装的Y2Co17纳米结构具有良好的结构稳定性和可切换的微波吸收

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-07 DOI: 10.1007/s12598-025-03470-0

Jie Ma, Han Zhang, Bai Yang, Xu-Feng Li, Rong-Hai Yu, Xi-Xiang Zhang, Ran Li

It is crucial to improve the antioxidant ability and structural stability of high-performance rare earth (RE) metal nanoalloys for their potential wide applications. In this work, an efficient functional surface carbon modification method has been provided to fabricate high-stability RE alloy/carbon nanostructures as high-performance electromagnetic materials. Specifically, graphite-encapsulated Y₂Co₁₇ nanoalloys constructed with high-purity Y₂Co₁₇ nanoparticles entirely coated with dense ultrathin N-doped graphite carbon (NGC) nanolayers to form antioxidative Y₂Co₁₇@NGC nanostructures are fabricated by a precisely controlled calcium thermic reduction of well-designed crystalline CoO-Co-Y₂O₃/C precursors. Another similarly structured Y₂Co₁₇@defect-rich graphite carbon (DGC) nanostructure is obtained by replacing NGC in Y₂Co₁₇@NGC with DGC by the same calcium thermic reduction but adjusting the carbon sources in the precursors. The excellent oxidation resistance and stable structures for these graphite-encapsulated Y₂Co₁₇ nanostructures facilitate the formation of ultrapure magnetic planar-anisotropy Y₂Co₁₇ phase, which results in their good soft magnetism with ultrahigh saturation magnetization values of 112.1–113.3 A m² kg⁻¹. Y₂Co₁₇@NGC nanostructures exhibit a favorable C band microwave absorption with a high minimum reflection loss (RL_min) value up to −80.16 dB at 4.30 GHz with a 4.03-mm-thick and Y₂Co₁₇@DGC nanostructures show a typical Ku band absorption with a RL_min value of −52.59 dB at 16.71 GHz with a 1.34 mm thickness. The good switchable electromagnetic properties of these graphite-encapsulated Y₂Co₁₇ nanostructures are demonstrated to arise from their different surface carbon defects. This work provides a surface carbon treatment strategy for fundamentally improving the oxidation resistance and structural stability of the easily oxidized RE nanoalloys and further constructing novelly structured functionalized RE alloy/carbon nanostructures.

提高高性能稀土金属纳米合金的抗氧化能力和结构稳定性是其广阔应用前景的关键。本研究为制备高性能电磁材料的高稳定性稀土合金/碳纳米结构提供了一种有效的表面功能碳改性方法。具体来说，石墨封装的Y2Co17纳米合金由高纯度的Y2Co17纳米颗粒完全包裹致密的超薄n掺杂石墨碳（NGC）纳米层构成，形成抗氧化的Y2Co17@NGC纳米结构，通过精确控制的钙热还原精心设计的晶体CoO-Co-Y2O3/C前驱体制备。采用相同的钙热还原方法，将Y2Co17@NGC中的NGC替换为DGC，但对前驱体中的碳源进行了调整，得到了另一种结构相似的Y2Co17@defect-rich石墨碳纳米结构。石墨包覆的Y2Co17纳米结构具有优异的抗氧化性能和稳定的结构，有利于形成平面各向异性超纯磁性Y2Co17相，具有良好的软磁性，饱和磁化强度达到112.1 ~ 113.3 A m2 kg−1。Y2Co17@NGC纳米结构表现出良好的C波段微波吸收，在4.30 GHz时，厚度为4.03 mm，最小反射损耗（RLmin）值高达- 80.16 dB； Y2Co17@DGC纳米结构表现出典型的Ku波段吸收，在16.71 GHz时，厚度为1.34 mm， RLmin值为- 52.59 dB。这些石墨包覆的Y2Co17纳米结构具有良好的可切换电磁性能，这是由于其不同的表面碳缺陷。本研究为从根本上提高易氧化稀土纳米合金的抗氧化性和结构稳定性，进一步构建结构新颖的功能化稀土合金/碳纳米结构提供了一种表面碳处理策略。

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引用次数: 0

Insights into effects of Co and Mn elements on the cycle stability of ultrahigh-nickel cathodes charged at same delithiation state Co和Mn元素对相同衰竭状态下超高镍阴极循环稳定性影响的研究

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-07 DOI: 10.1007/s12598-025-03469-7

Ling-Jun Li, Pan-Qing Wang, Niu Zhao, Xiao-Xue Tan, Ke-Chen Liu, Yu-Heng Wang, Tian-Xiang Ning, Lei Tan, Kang-Yu Zou

The introduction of Co and Mn is regarded as an effective strategy to enhance the cycling stability of LiNi_xM_1−xO₂ (x ≥ 0.9) cathodes. However, since the delithiation degrees of respective LiNi_xM_1−xO₂ cathodes measured at the fixed cutoff voltage are different, it is necessary to design the appropriate systems to evaluate the specific roles of Co and Mn elements in cyclic stability. Therefore, three LiNi_xM_1−xO₂ cathodes, including LiNiO₂ (LNO), LiNi_0.9Co_0.1O₂ (NC91), and LiNi_0.9Mn_0.1O₂ (NM91) have been chosen for systematically investigating the effect of Co and Mn on cycle durability, which are controlled at the same delithiation state during the electrochemical processes. It is found that the order of cycling stability among the three cathodes is NC91 > LNO > NM91 in the 80 mol% delithiation state. Co substitution suppresses lattice distortion, mitigates transition metal dissolution and structural degradation, further enhancing structural/interface stability, which brings out outstanding cycle stability of NC91. Notably, cycling stability is mainly determined by interfacial stability. Although NM91 exhibits superior structural stability compared to NC91, the worst cycling performance of NM91 is presented, which is attributed to the deteriorated interfacial stability resulting from the Jahn–Teller from Mn³⁺. This study elucidates the effect of Co and Mn on the cycle stability in LiNi_xM_1−xO₂ cathodes under the same delithiation state, thereby delivering reasonable guidance for designing advanced ultrahigh-nickel cathodes.

Graphical abstract

引入Co和Mn被认为是提高LiNixM1−xO2 （x≥0.9）阴极循环稳定性的有效策略。然而，由于在固定截止电压下测量的各自LiNixM1−xO2阴极的衰减程度不同，因此有必要设计合适的系统来评估Co和Mn元素在循环稳定性中的具体作用。因此，本文选择LiNiO2 （LNO）、LiNi0.9Co0.1O2 （NC91）和LiNi0.9Mn0.1O2 （NM91）三种LiNixM1−xO2阴极，系统研究了Co和Mn在电化学过程中控制在相同的电解状态下对循环耐久性的影响。在80 mol%衰减状态下，三种阴极的循环稳定性依次为NC91 >； LNO > NM91。Co取代抑制了晶格畸变，减轻了过渡金属的溶解和结构降解，进一步提高了结构/界面稳定性，使NC91具有出色的循环稳定性。值得注意的是，循环稳定性主要由界面稳定性决定。虽然NM91的结构稳定性优于NC91，但NM91的循环性能最差，这是由于Mn3+的Jahn-Teller导致界面稳定性恶化所致。本研究阐明了Co和Mn对相同衰竭状态下LiNixM1−xO2阴极循环稳定性的影响，从而为设计先进的超高镍阴极提供合理的指导。图形抽象

{"title":"Insights into effects of Co and Mn elements on the cycle stability of ultrahigh-nickel cathodes charged at same delithiation state","authors":"Ling-Jun Li, Pan-Qing Wang, Niu Zhao, Xiao-Xue Tan, Ke-Chen Liu, Yu-Heng Wang, Tian-Xiang Ning, Lei Tan, Kang-Yu Zou","doi":"10.1007/s12598-025-03469-7","DOIUrl":"10.1007/s12598-025-03469-7","url":null,"abstract":"<div><p>The introduction of Co and Mn is regarded as an effective strategy to enhance the cycling stability of LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> (<i>x</i> ≥ 0.9) cathodes. However, since the delithiation degrees of respective LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes measured at the fixed cutoff voltage are different, it is necessary to design the appropriate systems to evaluate the specific roles of Co and Mn elements in cyclic stability. Therefore, three LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes, including LiNiO<sub>2</sub> (LNO), LiNi<sub>0.9</sub>Co<sub>0.1</sub>O<sub>2</sub> (NC91), and LiNi<sub>0.9</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NM91) have been chosen for systematically investigating the effect of Co and Mn on cycle durability, which are controlled at the same delithiation state during the electrochemical processes. It is found that the order of cycling stability among the three cathodes is NC91 > LNO > NM91 in the 80 mol% delithiation state. Co substitution suppresses lattice distortion, mitigates transition metal dissolution and structural degradation, further enhancing structural/interface stability, which brings out outstanding cycle stability of NC91. Notably, cycling stability is mainly determined by interfacial stability. Although NM91 exhibits superior structural stability compared to NC91, the worst cycling performance of NM91 is presented, which is attributed to the deteriorated interfacial stability resulting from the Jahn–Teller from Mn<sup>3+</sup>. This study elucidates the effect of Co and Mn on the cycle stability in LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes under the same delithiation state, thereby delivering reasonable guidance for designing advanced ultrahigh-nickel cathodes.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8404 - 8415"},"PeriodicalIF":11.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ni, Co bimetallic MOF of dual-controlled by micro-morphology and unit cell structure for biomass-based self-supporting energy storage device Ni， Co双金属MOF的微形貌和单位电池结构双控制生物质自支撑储能装置

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-08-07 DOI: 10.1007/s12598-025-03506-5

Yongkang Zhang, Chuanyin Xiong, Qiancheng Xiong, Qing Xiong, Mengjie Zhao, Bo Wang, Mengxia Shen, Qiusheng Zhou, Yonghao Ni

Increasing the interlayer spacing of metal–organic frameworks (MOFs) through multi-metal ion doping has emerged as an effective strategy to enhance electrolyte-ion transport within the MOF unit cell, enabling the design of nickel-based MOF materials with high capacity and energy density. In this work, a series of NiCo-MOF-x (x = 1–5) were synthesized by incorporating Co²⁺ ions into Ni-MOF. The introduction of Co²⁺ modulated the unit cell structure and governed the stacking configuration of MOF nanosheets. At an optimal Ni/Co molar ratio of 4:1, the NiCo-MOF-2 sample demonstrates superior electrochemical performance, delivering a specific capacitance of 1238.6 F g⁻¹ at 0.2 A g⁻¹. Subsequently, NiCo-MOF-2 was grown in situ on carbonized wood (CW) to fabricate a NiCo-MOF@CW composite, which exhibits an areal capacitance of 4960 mF cm⁻² at 0.6 mA cm⁻². An asymmetric supercapacitor (NiCo-MOF@CW//AC) was assembled using NiCo-MOF@CW as the positive electrode and activated carbon (AC) as the negative electrode. The device achieves an areal energy density of 1.88 mWh cm⁻² at a power density of 2.88 mW cm⁻² (1 mA cm⁻²), with 83.6% capacitance retention after 2000 charge–discharge cycles. Notably, two serially connected NiCo-MOF@CW//AC devices successfully illuminate a red LED (operating voltage: 1.6–1.75 V) for 20 min. The multi-metal ion doping strategy combined with binder-free, self-supporting electrode architecture presents a novel approach for synthesizing high-performance energy storage materials.

Graphical abstract

通过多金属离子掺杂增加金属有机骨架（MOF）的层间间距已成为提高MOF单元电池内电解质离子传输的有效策略，使镍基MOF材料具有高容量和高能量密度。本文通过将Co2+离子掺入Ni-MOF中，合成了一系列NiCo-MOF-x （x = 1-5）。Co2+的引入调节了MOF纳米片的单胞结构，控制了MOF纳米片的堆叠构型。在最佳的Ni/Co摩尔比为4:1时，NiCo-MOF-2样品表现出优异的电化学性能，在0.2 a g−1时提供了1238.6 F g−1的比电容。随后，NiCo-MOF-2在碳化木材（CW）上原位生长，制备了NiCo-MOF@CW复合材料，该复合材料在0.6 mA cm -2下的面电容为4960 mF cm -2。以NiCo-MOF@CW为正极，活性炭（AC）为负极，组装了一个不对称超级电容器（NiCo-MOF@CW//AC）。该器件在2.88 mW cm - 2 （1 mA cm - 2）的功率密度下实现了1.88 mWh cm - 2的面能量密度，2000次充放电循环后电容保持率为83.6%。值得注意的是，两个串联的NiCo-MOF@CW//AC器件成功地照亮了一个红色LED（工作电压：1.6-1.75 V） 20分钟。多金属离子掺杂策略与无粘结剂、自支撑电极结构相结合，为合成高性能储能材料提供了一种新的途径。图形抽象

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引用次数: 0