Nickel Cobalt Sulfide Nanosheets on Cotton Fabric-Derived Carbon Substrates as Self-Standing Binder-Free Electrodes for Asymmetric All-Solid-State Supercapacitors

Abstract

Cobalt nickel sulfide (Ni-Co-S), a typical bimetallic sulfide, is regarded as a promising electrode material for supercapacitors (SCs). In this study, the electrodeposition process is employed to grow vertically aligned Ni-Co-S nanosheets on a carbon film (CF) substrate derived from cotton fabrics. The conductive and porous CF film not only ensures the uniform distribution of Ni-Co-S nanosheets but also offers an efficient pathway for the transportation of electrons and electrolyte ions. The Ni-Co-S nanosheet arrays, characterized by their small thickness and open pores, facilitate to provide a rapid diffusion path for electrolyte ions and expose sufficient active surfaces for charge storage. The synergistic effect resulting from the rational combination of Ni-Co-S nanosheets and the CF film substrate endows the film electrode with a high areal capacitance of 1800 mF cm⁻² at 2 mV s⁻¹ and remarkable mechanical flexibility. Furthermore, when an all-solid-state asymmetric SC device is assembled, a high energy density of 324.1 mWh cm⁻² is achieved at a power density of 2252.4 mW cm⁻².

Keywords

carbon fiber / cotton fabric / electrode / sulfide / supercapacitor

References

[1] Y.-N. Liu, L.-J. Feng, and S.-W. Bian, “Surface Structure Construction of Fibers in a Conductive Metal-Organic Framework/Metal/Cotton Electrode for Flexible Textile Supercapacitors,” ACS Applied Electronic Materials 4, no. 9 (2022): 4595-4604.

[2] Y.-L. Huang and S.-W. Bian, “Free-Standing Mxene/Carbon Nanotube@Fe₂O₃ Film Electrodes With High Capacitance for All-in-One Supercapacitors,” ACS Applied Energy Materials 7, no. 22 (2024): 10358-10366.

[3] Y.-L. Huang and S.-W. Bian, “Vacuum-Filtration Assisted Layer-by-Layer Strategy to Design MXene/Carbon Nanotube@MnO₂ All-in-One Supercapacitors,” Journal of Materials Chemistry A 9, no. 37 (2021): 21347-21356.

[4] L. Lin, H. Ning, S. Song, C. Xu, and N. Hu, “Flexible Electrochemical Energy Storage: The Role of Composite Materials,” Composites Science and Technology 192, no. 26 (2020): 108102.

[5] Y. Yue, Y.-L. Huang, and S.-W. Bian, “Nitrogen-Doped Hierarchical Porous Carbon Films Derived From Metal-Organic Framework/Cotton Composite Fabrics as Freestanding Electrodes for Flexible Supercapacitors,” ACS Applied Electronic Materials 3, no. 5 (2021): 2178-2186.

[6] R. Liu, S. Xu, X. Shao, et al., “Defect-Engineered NiCo-S Composite as a Bifunctional Electrode for High-Performance Supercapacitor and Electrocatalysis,” ACS Applied Materials & Interfaces 13, no. 40 (2021): 47717-47727.

[7] X. Li, W. Zhang, Z. Gu, et al., “Facile Fabrication of N-Doped RGO Decorated CoS₂ Nanoparticles as Advanced Integrated Electrode for Enhanced Supercapacitor Performance,” Electrochimica Acta 509 (2025): 145312.

[8] W. Chen, H. Quan, X. Chen, H. Wang, and D. Chen, “Carbon Quantum Dot Regulated Electrochemical Activation of Co_0.03Ni_0.97LDH for Energy Storage,” Inorganic Chemistry Frontiers 11, no. 3 (2024): 899-911.

[9] J. Rehman, K. Eid, R. Ali, et al., “Engineering of Transition Metal Sulfide Nanostructures as Efficient Electrodes for High-Performance Supercapacitors,” ACS Applied Energy Materials 5, no. 6 (2022): 6481-6498.

[10] H. Rong, T. Chen, R. Shi, Y. Zhang, and Z. Wang, “Hierarchical NiCo₂O₄@NiCo₂S₄ Nanocomposite on Ni Foam as an Electrode for Hybrid Supercapacitors,” ACS Omega 3, no. 5 (2018): 5634-5642.

[11] X. Wang, Y. Deng, Z. Wang, et al., “Sophora-Like Nickel-Cobalt Sulfide and Carbon Nanotube Composites in Carbonized Wood Slice Electrodes for All-Solid-State Supercapacitors,” ACS Applied Energy Materials 5, no. 6 (2022): 7400-7407.

[12] S.-C. Wang, D. Xiong, C. Chen, M. Gu, and F. Y. Yi, “The Controlled Fabrication of Hierarchical CoS₂@NiS₂ Core-Shell Nanocubes by Utilizing Prussian Blue Analogue for Enhanced Capacitive Energy Storage Performance,” Journal of Power Sources 450 (2020): 227712.

[13] X. Wang, T. Wang, R. Zhou, et al., “Ultrathin N_i1-xCo_xS₂ Nanoflakes as High Energy Density Electrode Materials for Asymmetric Supercapacitors,” Beilstein Journal of Nanotechnology 10 (2019): 2207-2216.

[14] L. Jin, B. Liu, Y. Wu, S. Thanneeru, and J. He, “Synthesis of Mesoporous CoS₂ and Ni_xCo₁-xS₂ With Superior Supercapacitive Performance Using a Facile Solid-Phase Sulfurization,” ACS Applied Materials & Interfaces 9, no. 42 (2017): 36837-36848.

[15] X. Chen, D. Chen, X. Guo, R. Wang, and H. Zhang, “Facile Growth of Caterpillar-Like NiCo₂S₄ Nanocrystal Arrays on Nickle Foam for High-Performance Supercapacitors,” ACS Applied Materials & Interfaces 9, no. 22 (2017): 18774-18781.

[16] Z. Wei, S. Tang, and Z. Tang, “Nickel-Cobalt-Sulfide Prepared by One-Step Electrodeposition on Expanded Graphite for High-Performance Supercapacitors,” Journal of Electronic Materials 49, no. 9 (2020): 5430-5438.

[17] J. Liu, M. Chen, L. Zhang, et al., “A Flexible Alkaline Rechargeable Ni/Fe Battery Based on Graphene Foam/Carbon Nanotubes Hybrid Film,” Nano Letters 14, no. 12 (2014): 7180-7187.

[18] C. Liu and X. Wu, “NiCo₂S₄ Nanotube Arrays Grown on Flexible Carbon Fibers as Battery-Type Electrodes for Asymmetric Supercapacitors,” Materials Research Bulletin 103 (2018): 55-62.

[19] H.-T. Wang, Y.-N. Liu, X.-H. Kang, et al., “Flexible Hybrid Yarn-Shaped Supercapacitors Based on Porous Nickel Cobalt Sulfide Nanosheet Array Layers on Gold Metalized Cotton Yarns,” Journal of Colloid and Interface Science 532 (2018): 527-535.

[20] Q. Song Jiang, W. Cheng, W. Li, et al., “One-Step Electrodeposition of Amorphous Nickel Cobalt Sulfides on FTO for High-Efficiency Dye-Sensitized Solar Cells,” Materials Research Bulletin 114 (2019): 10-17.

[21] A. Irshad and N. Munichandraiah, “Electrodeposited Nickel-Cobalt-Sulfide Catalyst for the Hydrogen Evolution Reaction,” ACS Applied Materials & Interfaces 9, no. 23 (2017): 19746-19755.

[22] L. Fu, Z. Liu, Y. Liu, et al., “Beaded Cobalt Oxide Nanoparticles Along Carbon Nanotubes: Towards More Highly Integrated Electronic Devices,” Advanced Materials 17, no. 2 (2005): 217-221.

[23] J. Xu, P. Gao, and T. S. Zhao, “Non-Precious Co₃O₄ Nano-Rod Electrocatalyst for Oxygen Reduction Reaction in Anion-Exchange Membrane Fuel Cells,” Energy & Environmental Science 5, no. 1 (2012): 5333-5339.

[24] F. Zhang, J. Ma, Y. Qin, Y. Wang, S. Xu, and R. Li, “Rational Construction of Ni-Co-S Nanosheets Encapsulated NiS₂ Micro-Blocks on Carbon Cloth as High-Performance Supercapacitor Electrode,” Materials Letters 262 (2020): 127021.

[25] F. Zhu, H. Xia, and T. Feng, “Nanowire Interwoven NiCo₂S₄ Nanowall Arrays as Promising Anodes for Lithium Ion Batteries,” supplement, Materials Technology 30, no. Suppl 2 (2015): A53-A57.

[26] T.-F. Yi, J.-J. Pan, T.-T. Wei, Y. Li, and G. Cao, “NiCo₂S₄-Based Nanocomposites for Energy Storage in Supercapacitors and Batteries,” Nano Today 33 (2020): 100894.

[27] W. Guo, J. Kim, H. Kim, and S. H. Ahn, “Direct Electrodeposition of Ni-Co-S on Carbon Paper as an Efficient Cathode for Anion Exchange Membrane Water Electrolysers,” International Journal of Energy Research 45, no. 2 (2021): 1918-1931.

[28] X. Li, Q. Li, Y. Wu, M. Rui, and H. Zeng, “Two-Dimensional, Porous Nickel-Cobalt Sulfide for High-Performance Asymmetric Supercapacitors,” ACS Applied Materials & Interfaces 7, no. 34 (2015): 19316-19323.

[29] M. Yu and X. Feng, “Thin-Film Electrode-Based Supercapacitors,” Joule 3, no. 2 (2019): 338-360.

[30] J. Jiang, Y. Sun, Y. Chen, et al., “One-Step Synthesis of Nickel Cobalt Sulfide Nanostructure for High-Performance Supercapacitor,” Journal of Materials Science 54, no. 18 (2019): 11936-11950.

[31] M. Dong, Z. Wang, X. Li, H. Guo, and J. Wang, “A Smart Architecture of Nickel-Cobalt Sulfide Nanotubes Assembled Nanoclusters for High-Performance Pseudocapacitor,” Journal of Alloys and Compounds 765 (2018): 505-511.

[32] M. Govindasamy, S. Shanthi, E. Elaiyappillai, et al., “Fabrication of Hierarchical NiCo₂S₄@CoS₂ Nanostructures on Highly Conductive Flexible Carbon Cloth Substrate as a Hybrid Electrode Material for Supercapacitors With Enhanced Electrochemical Performance,” Electrochimica Acta 293 (2019): 328-337.

[33] M. Sun, J. Tie, G. Cheng, et al., “In Situ Growth of Burl-Like Nickel Cobalt Sulfide on Carbon Fibers as High-Performance Supercapacitors,” Journal of Materials Chemistry A 3, no. 4 (2015): 1730-1736.

[34] X. Hong, J. Li, G. Zhu, et al., “Cobalt-Nickel Sulfide Nanosheets Modified by Nitrogen-Doped Porous Reduced Graphene Oxide as High-Conductivity Cathode Materials for Supercapacitor,” Electrochimica Acta 362 (2020): 137156.

[35] W. Zhao, Y. Zheng, L. Cui, et al., “MOF Derived Ni-Co-S Nanosheets on Electrochemically Activated Carbon Cloth via an Etching/Ion Exchange Method for Wearable Hybrid Supercapacitors,” Chemical Engineering Journal 371 (2019): 461-469.

[36] N. Van Hoa, P. A. Dat, N. Van Hieu, et al., “Rapid and Efficient Synthesis of High-Porous Reduced Graphene Oxide/NiCo₂S₄ Nanocomposites for Supercapacitor Application,” Diamond and Related Materials 106 (2020): 107850.

[37] Y. Chen, C. Jing, X. Fu, et al., “Synthesis of Porous NiCoS Nanosheets With Al Leaching on Ordered Mesoporous Carbon for High-Performance Supercapacitors,” Chemical Engineering Journal 384 (2020): 123367.

[38] G. K. Maron, M. G. Masteghin, V. Gehrke, et al., “Enhanced Pseudocapacitive Behaviour in Laser-Written Graphene Micro-Supercapacitors Decorated With Nickel Cobalt Sulphide Nanoparticles,” Materials Research Bulletin 168 (2023): 112490.

[39] S. Zhu, T. Li, V. K. Bandari, et al., “High Mass Loading Asymmetric Micro-Supercapacitors With Ultrahigh Areal Energy and Power Density,” ACS Applied Materials & Interfaces 13, no. 49 (2021): 58486-58497.

[40] J. Geng, Y. Jin, W. Tian, et al., “Nickel Cobalt Sulfides and Carbon Nanotube Intercalated Graphene Film Electrodes for High-Performance Flexible All-Solid-State Asymmetric Supercapacitors,” Journal of Energy Storage 98 (2024): 113178.

RIGHTS & PERMISSIONS

2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.