Journal of Materials Science

, Volume 54, Issue 6, pp 4905–4916 | Cite as

Hierarchical NiCo2−xFexO4/Ni2CoS4 nanoarray-decorated carbon textile anode with enhanced stability and capacitance

  • Zhaohui Liu
  • Chenhao Pan
  • Wen Li
  • Xiao Zhang
  • Longqiang Wang
  • Bo Lin
  • Shougang Chen
Energy materials


Subunits of one-dimensional (1D) NiCo2−xFexO4 nanotube and two-dimensional (2D) Ni2CoS4 nanosheet are integrated on carbon textile substrates through a hydrothermal method. With a unique structure and efficient usage of active materials, the prepared NiCo2−xFexO4/Ni2CoS4/carbon textile nanocomposites possess a high specific capacitance of 2220 F g−1 at 1 A g−1 and 91.8% of capacitance retention after 10,000 cycles. The prepared nanocomposites as positive electrode and the biomass carbon as negative electrode are assembled to form an asymmetric supercapacitor, with a maximum energy density of 62.63 Wh kg−1 at a power density of 160.82 W kg−1. The supercapacitor possesses an outstanding cycling stability of 81.6% retention after 10,000 cycles. Tailor-made hollow structure, which could provide sufficient space for the electrode to buffer volume changes due to expansion/contraction of the active material, holds a potential application for high-performance supercapacitors. The superior performance of the hierarchical nanocomposites makes it a promising electrode material for practical application in supercapacitors.



This work was supported by the National Natural Science Foundation (51572249) and the Fundamental Research Funds for the Central Universities (841562011).

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.

Supplementary material

10853_2018_3209_MOESM1_ESM.docx (2.3 mb)
Supplementary material 1 (DOCX 2368 kb)


  1. 1.
    Simon P, Gogotsi Y (2013) Capacitive energy storage in nanostructured carbon–electrolyte systems. Acc Chem Res 46:1094–1103CrossRefGoogle Scholar
  2. 2.
    Trudeau M-L (1999) Advanced materials for energy storage. MRS Bull 24:23–26CrossRefGoogle Scholar
  3. 3.
    Wang Y, Xia Y (2013) Recent progress in supercapacitors: from materials design to system construction. Adv Mater 25:5336–5342CrossRefGoogle Scholar
  4. 4.
    Wang M, Jin F-D, Zhang X-J, Wang J, Huang S-F, Zhang X-Y, Mu S-C, Zhao Y-P, Zhao Y-F (2017) Multihierarchical structure of hybridized phosphates anchored on reduced graphene oxide for high power hybrid energy storage devices. ACS Sustain Chem Eng 5:5679–5685CrossRefGoogle Scholar
  5. 5.
    Chen Z-Y, Xiong D-B, Zhang X-J, Ma H-N, Xia M-R, Zhao Y-F (2016) Construction of a novel hierarchical structured NH4–Co–Ni phosphate toward an ultrastable aqueous hybrid capacitor. Nanoscale 8:6636–6645CrossRefGoogle Scholar
  6. 6.
    Ma H-N, He J, Xiong D-B, Wu J-S, Li Q-Q, Dravid V-Y, Zhao Y-F (2016) Nickel cobalt hydroxide@reduced graphene oxide hybrid nanolayers for high performance asymmetric supercapacitors with remarkable cycling stability. ACS Appl Mater Interfaces 8:1992–2000CrossRefGoogle Scholar
  7. 7.
    Zhao Y-F, Zhang X-J, He J, Zhang L, Xia M-R, Gao F-M (2015) Morphology controlled synthesis of nickel cobalt oxide for supercapacitor application with enhanced cycling stability. Electrochim Acta 174:51–56CrossRefGoogle Scholar
  8. 8.
    He X, Liu Q, Liu J, Li R, Zhang H, Chen R, Wang J (2017) High-performance all-solid-state asymmetrical supercapacitors based on petal-like NiCo2S4/polyaniline nanosheets. Chem Eng J 325:134–143CrossRefGoogle Scholar
  9. 9.
    Liu X, Wu Z, Yin Y (2017) Hierarchical NiCo2S4@PANI core/shell nanowires grown on carbon fiber with enhanced electrochemical performance for hybrid supercapacitors. Chem Eng J 323:330–339CrossRefGoogle Scholar
  10. 10.
    bin Mohd Yusoff AR (2015) Graphene-based energy devices. In: Agrawal R, Chen C, Hao Y, Song Y, Wang C (eds) Graphene for supercapacitors. Weily, Singapore, pp 171–174Google Scholar
  11. 11.
    Frackowiak E (2007) Carbon materials for supercapacitor application. Phys Chem Chem Phys 9:1774–1785CrossRefGoogle Scholar
  12. 12.
    Futaba D-N, Hata K, Yamada T, Hiraoka T, Hayamizu Y, Kakudate Y, Tanaike O, Hatori H, Yumura M, Iijima S (2006) Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat Mater 5:987–994CrossRefGoogle Scholar
  13. 13.
    Tong Z, Yang Y, Wang J, Zhao J, Su B-L, Li Y (2014) Layered polyaniline/graphene film from sandwich-structured polyaniline/graphene/polyaniline nanosheets for high-performance pseudosupercapacitors. J Mater Chem A 2:4642–4651CrossRefGoogle Scholar
  14. 14.
    Yuan L, Yao B, Hu B, Huo K, Chen W, Zhou J (2013) Polypyrrole-coated paper for flexible solid-state energy storage. Energy Environ Sci 6:470–476CrossRefGoogle Scholar
  15. 15.
    Srither S-R, Karthik A, Arunmetha S, Murugesan D, Rajendran V (2016) Electrochemical supercapacitor studies of porous MnO2 nanoparticles in neutral electrolytes. Mater Chem Phys 183:375–382CrossRefGoogle Scholar
  16. 16.
    Tummala R, Guduru R-K, Mohanty P-S (2012) Nanostructured Co3O4 electrodes for supercapacitor applications from plasma spray technique. J Power Sources 209:44–51CrossRefGoogle Scholar
  17. 17.
    Wang B, Chen J-S, Wang Z, Madhavi S, Lou X-W (2012) green synthesis of NiO nanobelts with exceptional pseudo-capacitive properties. Adv Energy Mater 2:1188–1192CrossRefGoogle Scholar
  18. 18.
    Wang H, Casalongue H-S, Liang Y, Dai H (2010) Ni(OH)2 nanoplates grown on graphene as advanced electrochemical pseudocapacitor materials. J Am Chem Soc 132:7472–7477CrossRefGoogle Scholar
  19. 19.
    Jiang J, Li Y, Liu J, Huang X, Yuan C, Lou X-W (2012) Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage. Adv Mater 24:5166–5180CrossRefGoogle Scholar
  20. 20.
    Kang J, Hirata A, Qiu H-J, Chen L, Ge X, Fujita T, Chen M (2014) Self-grown oxy-hydroxide@ nanoporous metal electrode for high-performance supercapacitors. Adv Mater 26:269–272CrossRefGoogle Scholar
  21. 21.
    Shen L, Wang J, Xu G, Li H, Dou H, Zhang X (2015) NiCo2S4 nanosheets grown on nitrogen-doped carbon foams as an advanced electrode for supercapacitors. Adv Energy Mater 5:1400977CrossRefGoogle Scholar
  22. 22.
    Wang K, Wu H, Meng Y, Wei Z (2014) Conducting polymer nanowire arrays for high performance supercapacitors. Small 10:14–31CrossRefGoogle Scholar
  23. 23.
    Zhou C, Zhang Y, Li Y, Liu J (2013) Construction of high-capacitance 3D CoO@polypyrrole nanowire array electrode for aqueous asymmetric supercapacitor. Nano Lett 13:2078–2085CrossRefGoogle Scholar
  24. 24.
    Gao G, Wu H-B, Ding S, Liu L-M, Lou X-W (2015) Hierarchical NiCo2O4 nanosheets grown on Ni nanofoam as high-performance electrodes for supercapacitors. Small 11:804–808CrossRefGoogle Scholar
  25. 25.
    Shen L, Che Q, Li H, Zhang X (2014) Mesoporous NiCo2O4 nanowire arrays grown on carbon textiles as binder-free flexible electrodes for energy storage. Adv Funct Mater 24:2630–2637CrossRefGoogle Scholar
  26. 26.
    Xu K, Yang J, Hu J (2018) Synthesis of hollow NiCo2O4 nanospheres with large specific surface area for asymmetric supercapacitors. J Colloid Interface Sci 511:456–462CrossRefGoogle Scholar
  27. 27.
    Hu H, Guan B, Xia B, Lou X-W (2015) Designed formation of Co3O4/NiCo2O4 double-shelled nanocages with enhanced pseudocapacitive and electrocatalytic properties. J Am Chem Soc 137:5590–5595CrossRefGoogle Scholar
  28. 28.
    Jabeen N, Xia Q, Yang M, Xia H (2016) Unique core–shell nanorod arrays with polyaniline deposited into mesoporous NiCo2O4 support for high-performance supercapacitor electrodes. ACS Appl Mater Interfaces 8:6093–6100CrossRefGoogle Scholar
  29. 29.
    Li X, Sun W, Wang L, Qi Y, Guo T, Zhao X, Yan X (2015) Three-dimensional hierarchical self-supported NiCo2O4/carbon nanotube core–shell networks as high performance supercapacitor electrodes. RSC Adv 5:7976–7985CrossRefGoogle Scholar
  30. 30.
    Chen Q, Cai D, Zhan H (2017) Interconnected Ni–Co sulfide nanosheet arrays grown on nickel foam as binder-free electrodes for supercapacitors with high areal capacitance. J Alloys Compd 721:205–212CrossRefGoogle Scholar
  31. 31.
    Wei C, Huang Y, Xue S, Zhang X, Chen X, Yan J, Yao W (2017) One-step hydrothermal synthesis of flaky attached hollow-sphere structure NiCo2S4 for electrochemical capacitor application. Chem Eng J 317:873–881CrossRefGoogle Scholar
  32. 32.
    Peng S, Li L, Li C, Tan H, Cai R, Yu H, Mhaisalkar S, Srinivasan M, Ramakrishna S, Yan Q (2013) In situ growth of NiCo2S4 nanosheets on graphene for high-performance supercapacitors. Chem Commun 49:10178–10180CrossRefGoogle Scholar
  33. 33.
    Wen Y, Peng S, Wang Z, Hao J, Qin T, Lu S, Zhang J, He D, Fan X, Cao G (2017) Facile synthesis of ultrathin NiCo2S4 nano-petals inspired by blooming buds for high-performance supercapacitors. J Mater Chem A 5:7144–7152CrossRefGoogle Scholar
  34. 34.
    Hao P, Tian J, Sang Y, Tuan C-C, Cui G, Shi X, Wong C, Tang B, Liu H (2016) 1D Ni–Co oxide and sulfide nanoarray/carbon aerogel hybrid nanostructures for asymmetric supercapacitors with high energy density and excellent cycling stability. Nanoscale 8:16292–16301CrossRefGoogle Scholar
  35. 35.
    Yu L, Zhang L, Wu H-B, Lou X-W (2014) Formation of NixCo3−xS4 hollow nanoprisms with enhanced pseudocapacitive properties. Angew Chem Int Ed 126:3785–3788CrossRefGoogle Scholar
  36. 36.
    Zhu T, Wang Z, Ding S, Chen J-S, Lou X-W (2011) Hierarchical nickel sulfide hollow spheres for high performance supercapacitors. RSC Adv 1:397–400CrossRefGoogle Scholar
  37. 37.
    Hong W, Wang J, Li Z, Yang S (2015) Fabrication of Co3O4@Co–Ni sulfides core/shell nanowire arrays as binder-free electrode for electrochemical energy storage. Energy 93:435–441CrossRefGoogle Scholar
  38. 38.
    Yang J, Yu C, Fan X, Liang S, Li S, Huang H, Ling Z, Hao C, Qiu J (2016) Electroactive edge site-enriched nickel–cobalt sulfide into graphene frameworks for high-performance asymmetric supercapacitors. Energy Environ Sci 9:1299–1307CrossRefGoogle Scholar
  39. 39.
    Liu Z-H, Wang L-Q, Cheng Y-F, Cheng X-Y, Lin B, Yue L-F, Chen S-G (2018) Facile synthesis of NiCo2−xFexO4 nanotubes/carbon textiles composites for high-performance electrochemical energy storage devices. ACS Appl Nano Mater 1:997–1002CrossRefGoogle Scholar
  40. 40.
    Liu L, Zhang H, Fang L, Mu Y, Wang Y (2016) Facile preparation of novel dandelion-like Fe-doped NiCo2O4 microspheres@ nanomeshes for excellent capacitive property in asymmetric supercapacitors. J Power Sources 327:135–144CrossRefGoogle Scholar
  41. 41.
    Wu X, Han Z, Zheng X, Yao S, Yang X, Zhai T (2016) Core–shell structured Co3O4 @NiCo2O4 electrodes grown on flexible carbon fibers with superior electrochemical properties. Nano Energy 31:410–417CrossRefGoogle Scholar
  42. 42.
    Cao L, Tang G, Mei J, Liu H (2017) Construct hierarchical electrode with NixCo3−xS4 nanosheet coated on NiCo2O4 nanowire arrays grown on carbon fiber paper for high-performance asymmetric supercapacitors. J Power Sources 359:262–269CrossRefGoogle Scholar
  43. 43.
    Zhang X, Zheng Y, Zheng W, Zhao W, Chen D (2017) Graphite felt decorated with porous NiCo2O4 nanosheets for high-performance pseudocapacitor electrodes. J Mater Sci 52:5179–5187. CrossRefGoogle Scholar
  44. 44.
    Wang S-Q, Cai X, Song Y, Sun X-Q, Liu X-X (2018) VOx@MoO3 nanorod composite for high-performance supercapacitors. Adv Funct Mater 28:1803901CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Material Science and EngineeringOcean University of ChinaQingdaoPeople’s Republic of China
  2. 2.State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular EngineeringQingdao University of Science and TechnologyQingdaoPeople’s Republic of China

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