Preparation of Co₃S₄/rGO composites and their supercapacitor performances

Abstract

Graphene, with its two-dimensional structure, offers high mechanical flexibility and excellent conductivity, but its tendency to stack and aggregate in practical applications reduces the effective surface area, resulting in rapid capacity degradation. To overcome this, we in situ grow rod-like Co₃S₄ structures on graphene oxide graphene oxide (rGO), forming a highly conductive and mechanically stable composite. The Co₃S₄ nanoparticles serve as active sites for redox reactions, significantly improving the specific capacitance, while the rGO matrix enhances electron transport and mitigates the issues of volume expansion during charge/discharge cycles. The Co₃S₄/rGO composite is synthesized via a two-step hydrothermal process, and the effects of sulfuration temperature and time on electrochemical performance are systematically explored. The results show that the Co₃S₄/rGO-160-8 composite, synthesized at 160 °C for eight hours, achieves a specific capacitance of 1442.5 F·g^-1 at 1 A·g^-1 and exhibits a capacity retention of 93.3% after 5000 cycles at 4 A·g^-1. Furthermore, the Co₃S₄/rGO-160-8//activated carbon asymmetric supercapacitor delivers an energy density of 47.0 Wh·kg^-1 at 749.8 W·kg^-1 power density, with only an 8.9% capacity loss after 5000 cycles, demonstrating excellent cycling stability. This novel composite material offers a promising approach for high-performance supercapacitors, balancing high energy density, excellent rate performance, and long-term stability.

Keywords

Co₃S₄ / supercapacitor / electrochemical performance / composite materials

References

[1] Wang X,Xue Z.Sustainable development goals perspective of natural resources: does it paves the way for renewable sources of energy?.Resour Policy2023;86:104075

[2] Tian H,Cui X,Zhao E.RETRACTED: Multi-objective planning of microgrid based on renewable energy sources and energy storage system.J Energy Storage2023;68:107803

[3] Sahoo S,Sood A.Microwave-assisted synthesis of perovskite hydroxide-derived Co₃O₄/SnO₂/reduced graphene oxide nanocomposites for advanced hybrid supercapacitor devices.J Energy Storage2024;99:113321

[4] Sharma R,Kumar G.Progress and challenges in electrochemical energy storage devices: Fabrication, electrode material, and economic aspects.Chem Eng J2023;468:143706

[5] Zhang S,Du E.A review and outlook on cloud energy storage: An aggregated and shared utilizing method of energy storage system.Renew Sust Energy Rev2023;185:113606

[6] Zhu F,Gao Y.Molten salt electro-preparation of graphitic carbons.Exploration (Beijing)2023;3:20210186 PMCID:PMC10191008

[7] Yang W,Jian J.Metal organic framework-based materials for metal-ion batteries.Energy Storage Mater2024;66:103249

[8] Kumar R,Pandey R,Yadav RM.Electromagnetic irradiation-assisted synthesis, exfoliation and modification of graphene-based materials for energy storage and sensing applications.Mater Sci Eng: R: Rep2024;161:100860

[9] Wang T,Lei J,Wang H.Electrochemically induced surface reconstruction of Ni-Co oxide nanosheet arrays for hybrid supercapacitors.Exploration (Beijing)2021;1:20210178 PMCID:PMC10190942

[10] Naeem S,Shaikh AV.A review of cobalt-based metal hydroxide electrode for applications in supercapacitors.Adv Mater Sci Eng2023;2023:1-15

[11] Mishra S,Mishra AK.2H–MoS₂ nanoflowers based high energy density solid state supercapacitor.Mater Chem Phys2020;255:123551

[12] Zhou Y,Sun L.Multi-layer-stacked Co₉S₈ micro/nanostructure directly anchoring on carbon cloth as a flexible electrode in supercapacitors.Nanoscale2019;11:7457-64

[13] Ren H,Sun Y.Electrolyte engineering for the mass exfoliation of graphene oxide across wide oxidation degrees.J Mater Chem A2024;12:23416-24

[14] Yang J,Guo W,Zhang H.Electrochemical performances investigation of NiS/rGO composite as electrode material for supercapacitors.Nano Energy2014;5:74-81

[15] Jiang H,Hu Y,Li C.Nanostructured ternary nanocomposite of rGO/CNTs/MnO₂ for high-rate supercapacitors.ACS Sustainable Chem Eng2014;2:70-4

[16] Li H,Sun Z,Cheng H.A highly reversible Co₃S₄ microsphere cathode material for aluminum-ion batteries.Nano Energy2019;56:100-8

[17] Sahu N.MOF-derived Co₃S₄ nanoparticles embedded in nitrogen-doped carbon for electrochemical oxygen production.ACS Appl Nano Mater2023;6:7686-93

[18] Nandhini S.Co₃S₄-CoS/rGO hybrid nanostructure: promising material for high-performance and high-rate capacity supercapacitor.J Solid State Electrochem2021;25:465-77

[19] Wang Q,Du H,Wang Y.Co₃S₄ hollow nanospheres grown on graphene as advanced electrode materials for supercapacitors.J Mater Chem2012;22:21387

[20] Zhang Q,Lu B.Super-long life supercapacitors based on the construction of Ni foam/graphene/Co₃S₄ composite film hybrid electrodes.Electrochim Acta2014;132:180-5

[21] He G,Huangfu H.Enhanced electrochemical energy storage of rGO@Co_xS_y through nanostructural modulation.J Mater Sci: Mater Electron2021;32:13639-55

[22] Wu YQ,Yang Y.SnS₂ /Co₃S₄ hollow nanocubes anchored on S-doped graphene for ultrafast and stable Na-ion storage.Small2019;15:e1903873

[23] Yang YJ,Chen S.Assembly of Co₃S₄-encapsulated reduced graphene oxide nanosheets on Ni foam for binder-free supercapacitor electrode with boosted cycling stability.Ionics2023;29:2899-909

[24] Wei G,Huang H.The hetero-structured nanoarray construction of Co₃O₄ nanowires anchored on nanoflakes as a high-performance electrode for supercapacitors.Appl Surf Sci2021;538:147932

[25] Ma Q,Zhang J,Cui T.Surface engineering of Co₃O₄ nanoribbons forming abundant oxygen-vacancy for advanced supercapacitor.Appl Surf Sci2022;578:152001

[26] Zhao J,Wang Y,Peng Y.The application of nanostructured transition metal sulfides as anodes for lithium ion batteries.J Energy Chem2018;27:1536-54

[27] Nandhini S.The binder-free mesoporous CoNi₂S₄ electrode for high-performance symmetric and asymmetric supercapacitor devices.J Mater Sci2022;57:5933-53

[28] Ma Y,Yang W.Recent advances in transition metal oxides with different dimensions as electrodes for high-performance supercapacitors.Adv Compos Hybrid Mater2021;4:906-24

[29] Ma M,Wu Y.Progress and prospects of transition metal sulfides for sodium storage.Adv Fiber Mater2020;2:314-37

[30] Zhou J,Peng Y,Zeb A.Metal-organic framework-derived transition metal sulfides and their composites for alkali-ion batteries: a review.Coord Chem Rev2022;472:214781

[31] Xu M,Zhang T,Wang X.High-performance zeolitic imidazolate frameworks derived three- dimensional Co₃S₄/polyaniline nanocomposite for supercapacitors.J Energy Storage2021;35:102303

[32] Rakhi RB,Anjum DH.Nanostructured cobalt sulfide-on-fiber with tunable morphology as electrodes for asymmetric hybrid supercapacitors.J Mater Chem A2014;2:16190-8

[33] Yang C,Chen Q.Composites of NiCo layered double hydroxide nanosheets and Co₃S₄ nanoparticles for asymmetric supercapacitors.ACS Appl Nano Mater2023;6:10804-16

[34] Qiao Y,Li N,Jiao T.In situ-grown heterostructured Co₃S₄/CNTs/C nanocomposites with a bridged structure for high-performance supercapacitors.ACS Omega2021;6:33855-63 PMCID:PMC8675018

[35] Chen Q,Zhan H.Construction of reduced graphene oxide nanofibers and cobalt sulfide nanocomposite for pseudocapacitors with enhanced performance.J Alloys Compd2017;706:126-32