Sulfate-Substituted Na3V2(PO4)3 Nanodots Embedded in Carbon Nanotubes for Ultrafast Sodium-Ion Storage

IF 9.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nano Letters Pub Date : 2025-10-06 DOI:10.1021/acs.nanolett.5c03272

Naohisa Okita, Keisuke Matsumura, Yuta Harada, Masahiro Fukuyama, Mai Tomita, Masaya Nakagawa, Yuto Iwasaki, Akari Ukai, Kangkang Ge, Etsuro Iwama, Wako Naoi, Patrick Rozier, Patrice Simon, Katsuhiko Naoi

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Abstract

Polyanion-substituted sodium vanadium phosphate (Na₃V₂(PO₄)₃, NVP) derivatives, including SO₄, BO₃, WO₄, and SiO₄ substitutions, were systematically synthesized and impregnated with a nanocarbon network via ultracentrifugation. Among them, nanosized (5–30 nm), highly crystalline, and well-dispersed sulfate-substituted NVP (NVPS) nanodots were directly nucleated onto multiwalled carbon nanotubes, enabling ultrafast electrochemical kinetics. This nanoscale architecture delivered exceptional rate capability, achieving 97 mAh g^–1 at 1000C (3.6 s discharge), corresponding to 83% of the theoretical capacity, outperforming conventional NVP. The electrochemical kinetics analysis using a cavity microelectrode revealed reduced polarization, enhanced capacitive charge storage, and rapid sodium ion diffusion during intercalation/deintercalation, facilitated by the conformal interface between NVPS and MWCNT, possibly by sulfate-induced surface modifications. These findings establish polyanion substitution and ultracentrifugation-assisted materials processing as a transformative strategy for overcoming intrinsic transport limitations in NASICON-type phosphates, positioning NVPS as a benchmark material for next-generation high-power sodium-ion batteries and hybrid capacitors.

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碳纳米管中嵌入硫酸盐取代Na3V2(PO4)3纳米点的超快钠离子存储

系统合成了聚阴离子取代磷酸钒钠（Na3V2(PO4)3， NVP）衍生物，包括SO4， BO3， WO4和SiO4取代，并通过超离心浸渍纳米碳网络。其中，纳米尺寸（5-30 nm）、高结晶性、分散良好的硫酸盐取代NVP （NVPS）纳米点被直接成核到多壁碳纳米管上，实现了超快的电化学动力学。这种纳米级结构提供了卓越的倍率能力，在1000C （3.6 s放电）下达到97 mAh g-1，相当于理论容量的83%，优于传统的NVP。利用空腔微电极进行的电化学动力学分析表明，NVPS和MWCNT之间的保形界面可能是硫酸盐诱导的表面修饰，在插插/脱插过程中，NVPS和MWCNT之间的保形界面促进了极化降低、电容电荷存储增强和钠离子快速扩散。这些发现确立了聚阴离子取代和超离心辅助材料加工是克服nasicon型磷酸盐固有输运限制的变革策略，将NVPS定位为下一代高功率钠离子电池和混合电容器的基准材料。

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来源期刊

Nano Letters 工程技术-材料科学：综合

CiteScore

16.80

自引率

2.80%

发文量

1182

审稿时长

1.4 months

期刊介绍： Nano Letters serves as a dynamic platform for promptly disseminating original results in fundamental, applied, and emerging research across all facets of nanoscience and nanotechnology. A pivotal criterion for inclusion within Nano Letters is the convergence of at least two different areas or disciplines, ensuring a rich interdisciplinary scope. The journal is dedicated to fostering exploration in diverse areas, including: - Experimental and theoretical findings on physical, chemical, and biological phenomena at the nanoscale - Synthesis, characterization, and processing of organic, inorganic, polymer, and hybrid nanomaterials through physical, chemical, and biological methodologies - Modeling and simulation of synthetic, assembly, and interaction processes - Realization of integrated nanostructures and nano-engineered devices exhibiting advanced performance - Applications of nanoscale materials in living and environmental systems Nano Letters is committed to advancing and showcasing groundbreaking research that intersects various domains, fostering innovation and collaboration in the ever-evolving field of nanoscience and nanotechnology.