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

doi:10.19799/j.cnki.2095-4239.2025.0055

Abstract

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

CLC Number:

TM 911.1

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.

Figures/Tables 5

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Table 1

References 39

[1]	刘博宇, 庞青, 王腾飞, 等. 高镍三元正极材料LiNi_0.8Co_0.1Mn_0.1O₂在高压下的研究进展[J]. 储能科学与技术, 2024, 13(11): 3784-3795. DOI: 10.19799/j.cnki.2095-4239.2024.0432.
	LIU B Y, PANG Q, WANG T F, et al. Advancements in the modification of high-voltage Ni-rich ternary cathode material LiNi_0.8Co_0.1Mn_0.1O₂ for lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(11): 3784-3795. DOI: 10. 19799/j.cnki.2095-4239.2024.0432.
[2]	曾翠鸿, 陈秀娟, 李曼, 等. 钠离子电池P2-Na_0.6Li_0.27Mn_0.73O₂正极材料的W掺杂研究[J]. 储能科学与技术, 2024, 13(11): 3731-3741. DOI: 10.19799/j.cnki.2095-4239.2024.0511.
	ZENG C H, CHEN X J, LI M, et al. Investigation of W-doped P2-Na_0.6Li_0.27Mn_0.73O₂ cathode materials for sodium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(11): 3731-3741. DOI: 10.19799/j.cnki.2095-4239.2024.0511.
[3]	GUO K, WANG W, JIAO S Q. Recent progress and prospective on layered anode materials for potassium-ion batteries[J]. International Journal of Minerals, Metallurgy and Materials, 2022, 29(5): 1037-1052. DOI: 10.1007/s12613-022-2470-z.
[4]	WANG M, JIANG C L, ZHANG S Q, et al. Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage[J]. Nature Chemistry, 2018, 10(6): 667-672. DOI: 10.1038/s41557-018-0045-4.
[5]	WANG X S, DING J Y, CHEN J T, et al. Improved Li⁺ diffusion enabled by SEI film in a high-energy-density hybrid magnesium-ion battery[J]. Journal of Power Sources, 2019, 441: 227190. DOI: 10.1016/j.jpowsour.2019.227190.
[6]	SUN T J, NIAN Q S, ZHENG S B, et al. Layered Ca_0.28MnO₂·0.5H₂O as a high performance cathode for aqueous zinc-ion battery[J]. Small, 2020, 16(23): 2002852. DOI: 10.1002/smll.202002852.
[7]	LIN M C, GONG M, LU B G, et al. An ultrafast rechargeable aluminium-ion battery[J]. Nature, 2015, 520(7547): 324-328. DOI: 10.1038/nature14340.
[8]	DAS S K, MAHAPATRA S, LAHAN H. Aluminium-ion batteries: Developments and challenges[J]. Journal of Materials Chemistry A, 2017, 5(14): 6347-6367. DOI: 10.1039/C7TA00228A.
[9]	RAMASUBRAMANIAN B, DE A, KOPERSKI M, et al. State-of-the-art carbon cathodes with their intercalation chemistry, performance, and challenges for aluminum-ion batteries[J]. ACS Applied Energy Materials, 2025, 8(2): 683-698. DOI: 10.1021/acsaem.4c02431.
[10]	YANG H C, LI H C, LI J, et al. The rechargeable aluminum battery: Opportunities and challenges[J]. Angewandte Chemie International Edition, 2019, 58(35): 11978-11996. DOI: 10.1002/anie.201814031.
[11]	CHEN H C, JIANG J J, ZHANG L, et al. Highly conductive NiCo₂S₄ urchin-like nanostructures for high-rate pseudocapacitors[J]. Nanoscale, 2013, 5(19): 8879-8883. DOI: 10.1039/C3NR02958A.
[12]	XIAO J W, WAN L, YANG S H, et al. Design hierarchical electrodes with highly conductive NiCo₂S₄ nanotube arrays grown on carbon fiber paper for high-performance pseudocapacitors[J]. Nano Letters, 2014, 14(2): 831-838. DOI: 10.1021/nl404199v.
[13]	WEI C B, LIU H, GAN R H, et al. Flexible NiCo₂S₄-hollow carbon nanofibers electrocatalytic membrane as an advanced interlayer for lithium-sulfur batteries[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648: 129179. DOI: 10.1016/j.colsurfa.2022.129179.
[14]	YANG W W, LU H M, CAO Y, et al. Single-/few-layered ultrasmall WS₂ nanoplates embedded in nitrogen-doped carbon nanofibers as a cathode for rechargeable aluminum batteries[J]. Journal of Power Sources, 2019, 441: 227173. DOI: 10.1016/j.jpowsour. 2019.227173.
[15]	崔华敏, 掌学谦, 胡攀登, 等. 杯[4]醌/N掺杂的无定形碳纳米纤维复合材料储锂性能[J]. 应用化学, 2020, 37(2): 198-204. DOI: 10. 11944/j.issn.1000-0518.2020.02.190236.
	CUI H M, ZHANG X Q, HU P D, et al. Calix [4] quinone/N-doped amorphous carbon nanofibers composites for lithium-ion batteries[J]. Chinese Journal of Applied Chemistry, 2020, 37(2): 198-204. DOI: 10.11944/j.issn.1000-0518.2020.02.190236.
[16]	ZHANG W M, CHEN J T, LIU Y Q, et al. Decoration of hollow nitrogen-doped carbon nanofibers with tapered rod-shaped NiCo₂S₄ as a 3D structural high-rate and long-lifespan self-supported anode material for potassium-ion batteries[J]. Journal of Alloys and Compounds, 2020, 823: 153631. DOI: 10.1016/j.jallcom.2019.153631.
[17]	LI L, ZHANG X, LIU S A, et al. One-step hydrothermal synthesis of NiCo₂S₄ loaded on electrospun carbon nanofibers as an efficient counter electrode for dye-sensitized solar cells[J]. Solar Energy, 2020, 202: 358-364. DOI: 10.1016/j.solener.2020.03.110.
[18]	SIVANANTHAM A, GANESAN P, SHANMUGAM S. Bifunctional electrocatalysts: Hierarchical NiCo₂S₄ nanowire arrays supported on Ni foam: An efficient and durable bifunctional electrocatalyst for oxygen and hydrogen evolution reactions[J]. Advanced Functional Materials, 2016, 26(26): 4660. DOI: 10.1002/adfm. 201670166.
[19]	LI S J, GE P, JIANG F, et al. The advance of nickel-cobalt-sulfide as ultra-fast/high sodium storage materials: The influences of morphology structure, phase evolution and interface property[J]. Energy Storage Materials, 2019, 16: 267-280. DOI: 10.1016/j.ensm.2018.06.006.
[20]	BUAN M E M, MUTHUSWAMY N, WALMSLEY J C, et al. Nitrogen-doped carbon nanofibers for the oxygen reduction reaction: Importance of the iron growth catalyst phase[J]. ChemCatChem, 2017, 9(9): 1663-1674. DOI: 10.1002/cctc.2016 01585.
[21]	BŁOŃSKI P, TUČEK J, SOFER Z, et al. Doping with graphitic nitrogen triggers ferromagnetism in graphene[J]. Journal of the American Chemical Society, 2017, 139(8): 3171-3180. DOI: 10. 1021/jacs.6b12934.
[22]	YANG W W, LU H M, CAO Y, et al. A flexible free-standing cathode based on graphene-like MoSe₂ nanosheets anchored on N-doped carbon nanofibers for rechargeable aluminum-ion batteries[J]. Ionics, 2020, 26(7): 3405-3413. DOI: 10.1007/s115 81-020-03476-x.
[23]	WANG S, JIAO S Q, WANG J X, et al. High-performance aluminum-ion battery with CuS@C microsphere composite cathode[J]. ACS Nano, 2017, 11(1): 469-477. DOI: 10.1021/acsnano.6b06446.
[24]	LI J, LUO W B, ZHANG Z, et al. ZnSe/SnSe₂ hollow microcubes as cathode for high performance aluminum ion batteries[J]. Journal of Colloid and Interface Science, 2023, 639: 124-132. DOI: 10.1016/j.jcis.2023.02.057.
[25]	WANG S, YU Z J, TU J G, et al. A novel aluminum-ion battery: Al/AlCl₃-[EMIm] Cl/Ni₃S₂@Graphene[J]. Advanced Energy Materials, 2016, 6(13): 1600137. DOI: 10.1002/aenm.201600137.
[26]	ZHANG K Q, LEE T H, CHA J H, et al. Properties of CoS₂/CNT as a cathode material of rechargeable aluminum-ion batteries[J]. Electronic Materials Letters, 2019, 15(6): 727-732. DOI: 10.1007/s13391-019-00169-0.
[27]	LI J F, HUI K S, ZHENG Y S, et al. Stabilizing anionic redox processes in electrospun NiS₂-based cathode towards durable aluminum-ion batteries[J]. Chemical Engineering Journal, 2022, 450: 138237. DOI: 10.1016/j.cej.2022.138237.
[28]	YU Z J, KANG Z P, HU Z Q, et al. Hexagonal NiS nanobelts as advanced cathode materials for rechargeable Al-ion batteries[J]. Chemical Communications, 2016, 52(68): 10427-10430. DOI: 10.1039/C6CC05974K.
[29]	WU L, SUN R M, XIONG F Y, et al. A rechargeable aluminum-ion battery based on a VS₂ nanosheet cathode[J]. Physical Chemistry Chemical Physics, 2018, 20(35): 22563-22568. DOI: 10.1039/C8CP04772C.
[30]	LI H C, YANG H C, SUN Z H, et al. A highly reversible Co₃S₄ microsphere cathode material for aluminum-ion batteries[J]. Nano Energy, 2019, 56: 100-108. DOI: 10.1016/j.nanoen.2018.11.045.
[31]	LI Z Y, NIU B B, LIU J, et al. Rechargeable aluminum-ion battery based on MoS₂ microsphere cathode[J]. ACS Applied Materials & Interfaces, 2018, 10(11): 9451-9459. DOI: 10.1021/acsami.8b00100.
[32]	ZHOU Q P, WANG D W, NI L B, et al. Willow leaf-shape ReSe₂@C as positive electrode material for aluminum-ion batteries[J]. Journal of Alloys and Compounds, 2022, 909: 164773. DOI: 10.1016/j.jallcom.2022.164773.
[33]	ZHANG X F, WANG S, TU J G, et al. Flower-like vanadium suflide/reduced graphene oxide composite: An energy storage material for aluminum-ion batteries[J]. ChemSusChem, 2018, 11(4): 709-715. DOI: 10.1002/cssc.201702270.
[34]	ZHUANG R Y, MIAO G, HUANG Z L, et al. Non-stoichiometric CoS_1.097 nanoparticles prepared from CoAl-layered double hydroxide and MOF template as cathode materials for aluminum-ion batteries[J]. Journal of Energy Chemistry, 2021, 54: 639-643. DOI: 10.1016/j.jechem.2020.06.047.
[35]	ZHAO Z C, HU Z Q, LI Q, et al. Designing two-dimensional WS₂ layered cathode for high-performance aluminum-ion batteries: From micro-assemblies to insertion mechanism[J]. Nano Today, 2020, 32: 100870. DOI: 10.1016/j.nantod.2020.100870.
[36]	GRINDAL A, AZIMI G. Advancing aluminum-ion batteries: Unraveling the charge storage mechanisms of cobalt sulfide cathodes[J]. Scientific Reports, 2024, 14: 28468. DOI: 10.1038/s41598-024-78437-9.
[37]	ZHOU J S, SONG H H, MA L L, et al. Magnetite/graphene nanosheet composites: Interfacial interaction and its impact on the durable high-rate performance in lithium-ion batteries[J]. RSC Advances, 2011, 1(5): 782-791. DOI: 10.1039/C1RA00402F.
[38]	LI W W, MA Q B, SHEN P F, et al. Yolk-shell structured CuSi₂P₃@Graphene nanocomposite anode for long-life and high-rate lithium-ion batteries[J]. Nano Energy, 2021, 80: 105506. DOI: 10.1016/j.nanoen.2020.105506.
[39]	ZHANG Y, LIU S Q, JI Y J, et al. Emerging nonaqueous aluminum-ion batteries: Challenges, status, and perspectives[J]. Advanced Materials, 2018, 30(38): 1706310. DOI: 10.1002/adma.201706310.

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

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 39

Related Articles 4

Recommended Articles

Metrics

Comments

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]

[1]	Xunchang JIANG, Kelin YU, Daxiang YANG, Minhui LIAO, Yang ZHOU. Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries [J]. Energy Storage Science and Technology, 2025, 14(1): 1-12.
[2]	Yuedi WANG, Zhongzhu QIU, Miao WU, Yanyan ZHU, Meng QU. Preparation and electrochemical properties of porous NiMoO₄/NiCo₂S₄ composites [J]. Energy Storage Science and Technology, 2023, 12(4): 1034-1044.
[3]	Rui YANG, Lili WANG, Yiming MI, Ye LIU, Jianbao WU, Xinxin ZHAO. Research progress of transition metal oxides /C composite nanofibers fabricated by electrospinning in anode materials for lithium-ion batteries [J]. Energy Storage Science and Technology, 2021, 10(4): 1253-1260.
[4]	NI Qiao, WU Chuan, BAI Ying, LIU Yuanchang, CHEN Guanghai, WU Feng . Na₃V₂(PO₄)₃/C cathode materials with preferred（113）orientation for sodium ion batteries [J]. Energy Storage Science and Technology, 2016, 5(3): 341-348.