柔性自支撑NiCo2S4@氮掺杂碳纳米纤维的制备及其储铝性能研究

doi:10.19799/j.cnki.2095-4239.2025.0055

摘要/Abstract

摘要：

可充电铝离子电池有望成为新一代低成本、高比能、高安全性的电化学储能系统，缺乏合适的正极材料是制约铝离子电池发展的主要因素之一。本工作采用静电纺丝结合热处理制备了氮掺杂碳纳米纤维(N-CNFs)，将其作为水热反应基底负载双金属硫化物，获得了柔性自支撑NiCo₂S₄@N-CNFs复合结构。借助扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能谱分析(EDS)、X射线衍射(XRD)和X射线光电子能谱(XPS)等表征测试方法对其组成结构和形貌进行表征。将其直接作为铝离子电池的正极，通过恒电流充放电和循环伏安法(CV)对其比容量、循环稳定性以及倍率性能等电化学性能进行测试。结果表明，NiCo₂S₄@N-CNFs中，NiCo₂S₄呈花椰菜状，均匀地包裹在N-CNFs上，形成柔性自支撑结构，可直接作为铝离子电池的正极。在100 mA/g电流密度下，比容量可达到266.3 mAh/g，200次循环后，放电比容量仍可保持在151.6 mAh/g，表现出高比容量和优异的循环性能。在倍率性能测试中，经历了一系列较大的电流冲击后，比容量仍可恢复，表现出良好的倍率性能。通过分析充放电状态下NiCo₂S₄@N-CNFs的XRD以及Ni和Co的价态变化，证明了NiCo₂S₄的储铝机理为Ni和Co通过双金属协同效应共同完成Al³⁺的可逆嵌入与脱嵌。本研究为构建高性能铝离子电池正极材料提供了理论基础和设计依据。

关键词: 静电纺丝, 氮掺杂碳纳米纤维, NiCo₂S₄, 柔性自支撑, 铝离子电池

Abstract:

Rechargeable aluminum-ion batteries (AIBs) are regarded as promising next-generation electrochemical energy storage systems due to their high capacity, low cost, and enhanced safety. However, the development of high-performance cathode materials remains a critical challenge for the commercialization of AIBs. In this study, nitrogen-doped carbon nanofibers (N-CNFs) were synthesized via electrospinning and subsequent annealing, serving as substrates for a hydrothermal process to uniformly load bimetallic sulfide, resulting in a flexible, free-standing NiCo₂S₄@N-CNF composite. The composition, structure, and morphology were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy. The NiCo₂S₄@N-CNF composite was directly employed as a cathode for AIBs, and its specific capacity, cycling stability, and rate performance were evaluated through constant current charge-discharge tests and cyclic voltammetry. The results demonstrate that the cauliflower-like NiCo₂S₄ is uniformly wrapped on the N-CNFs, forming a flexible, free-standing structure suitable for direct use as a cathode in AIBs. At a current density of 100 mA/g, the specific capacity reached 266.3 mA h/g, and after 200 cycles, it maintained a discharge capacity of 151.6 mAh/g, indicating excellent specific capacity and cycling stability. Moreover, in rate performance tests, the specific capacity recovered well after high current shocks, demonstrating good rate capability. Analysis of XRD patterns and valence state changes of Ni and Co during charge and discharge confirmed that the aluminum storage mechanism in NiCo₂S₄ involves the reversible intercalation and de-intercalation of Al³⁺ ions facilitated by the bimetallic synergistic effect. This study provides theoretical guidance and a design reference for the development of high-performance cathode materials for AIBs.

Key words: electrospinning, nitrogen-doped carbon nanofibers, NiCo₂S₄, flexible free-standing, aluminum-ion batterie

中图分类号:

TM 911.1

杨文文, 刘建学, 邓佳瑶. 柔性自支撑NiCo₂S₄@氮掺杂碳纳米纤维的制备及其储铝性能研究[J]. 储能科学与技术, 2025, 14(9): 3269-3278.

Wenwen YANG, Jianxue LIU, Jiayao DENG. Flexible free-standing NiCo₂S₄@N-doped carbon nanofiber composite cathode for rechargeable aluminum-ion batteries[J]. Energy Storage Science and Technology, 2025, 14(9): 3269-3278.

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柔性自支撑NiCo₂S₄@氮掺杂碳纳米纤维的制备及其储铝性能研究

Flexible free-standing NiCo₂S₄@N-doped carbon nanofiber composite cathode for rechargeable aluminum-ion batteries

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参考文献 39

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正极活性材料	电流密度/(mA/g)	循环次数	比容量/(mAh/g)	参考文献
ZnSe/SnSe₂空心微立方	100	150	124	[24]
Ni₃S₂@石墨烯	100	100	60	[25]
CoS₂/碳纳米管	100	100	60	[26]
NiS₂/S掺杂碳纳米纤维	500	500	53	[27]
NiS纳米带	200	100	104.4	[28]
VS₂/石墨烯纳米片	100	50	50	[29]
Co₃S₄微球	50	150	90	[30]
MoS₂微球	40	100	66.7	[31]
ReSe₂@碳	100	1000	88	[32]
CuS@碳微球	20	100	90	[23]
VS₄/还原氧化石墨烯	100	100	93	[33]
CoS_1.097@碳	100	500	80	[34]
二维WS₂纳米片	1000	500	119	[35]

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