Hierarchical NiCo LDH–rGO/Ni Foam Composite as Electrode Material for High-Performance Supercapacitors

Abstract

In this study, a bulk composite material symbolized as NiCo LDH–rGO/Ni F was developed by a solvothermal process for the first time. This material was fabricated through simultaneous growth of nickel–cobalt layered double hydroxide (NiCo LDH) and reduced graphene oxide (rGO) on nickel foam. This bulk composite can be used directly as a binder-free electrode for supercapacitors (SCs). The physicochemical properties of this composite were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The electrochemical properties of the composite were measured by the cyclic voltammetry and galvanostatic charge–discharge. The results show that this composite had a hierarchical structure and exhibited a significantly enhanced specific capacitance of up to 3383 F/g at 1 A/g. The asymmetric SC using this composite as a positive electrode had a high energy density of 40.54 Wh/kg at the power density of 206.5 W/kg and good cycling stability. Owing to the synergies between the metal oxides and the rGO, the preparation method of in situ growth and its hierarchical structure, this bulk composite displayed excellent electrochemical performance and had a promising application as an efficient electrode for high-performance SCs.

Keywords

NiCo LDH–rGO / Hierarchical structure / Supercapacitors / In-situ growth

References

[1] Winter M, Brodd RJ. What are batteries, fuel cells, and supercapacitors?. Chem Rev, 2004, 104(10): 4245-4270.

[2] Conway BE. Electrochemical supercapacitors: scientific fundamentals and technological applications, 1999, New York, USA: Springer

[3] Frackowiak E, Beguin F. Electrochemical storage of energy in carbon nanotubes and nanostructured carbons. Carbon, 2002, 40(10): 1775-1787.

[4] Raccichini R, Varzi A, Passerini S, et al. The role of graphene for electrochemical energy storage. Nat Mater, 2015, 14(3): 271-279.

[5] Xia C, Chen W, Wang X, et al. Highly stable supercapacitors with conducting polymer core-shell electrodes for energy storage applications. Adv Energy Mater, 2015, 5(8): 1401805

[6] Hu CC, Chang KH, Lin MC, et al. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO₂ for next generation supercapacitors. Nano Lett, 2006, 6(12): 2690-2695.

[7] Gao G, Wu HB, Ding S, et al. Hierarchical NiCo₂O₄ nanosheets grown on Ni nanofoam as high-performance electrodes for supercapacitors. Small, 2015, 11(7): 804-808.

[8] Conway BE, Birss V, Wojtowicz J. The role and utilization of pseudocapacitance for energy storage by supercapacitors. J Power Sources, 1997, 66(1–2): 1-14.

[9] Poizot P, Laruelle S, Grugeon S, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature, 2001, 407(6803): 496-499.

[10] Wu ZS, Wang DW, Ren W, et al. Anchoring hydrous RuO₂ on graphene sheets for high-performance electrochemical capacitors. Adv Funct Mater, 2010, 20(20): 3595-3602.

[11] Hao Q, Xia X, Lei W, et al. Facile synthesis of sandwich-like polyaniline/boron-doped graphene nano hybrid for supercapacitors. Carbon, 2015, 81: 552-563.

[12] Xia XH, Chao DL, Zhang YQ, et al. Three-dimensional graphene and their integrated electrodes. Nano Today, 2014, 9(6): 785-807.

[13] Bonaccorso F, Colombo L, Yu G, et al. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science, 2015, 347(6217): 1246501

[14] Pu J, Tong Y, Wang S, et al. Nickel–cobalt hydroxide nanosheets arrays on Ni foam for pseudocapacitor applications. J Power Sources, 2014, 250: 250-256.

[15] Xing C, Musharavati F, Li H, et al. Synthesis, characterization, and properties of nickel–cobalt layered double hydroxide nanostructures. RSC Adv, 2017, 7(62): 38945-38950.

[16] Dong S, Dao AQ, Zheng B, et al. One-step electrochemical synthesis of three-dimensional graphene foam loaded nickel–cobalt hydroxides nanoflakes and its electrochemical properties. Electrochim Acta, 2015, 152: 195-201.

[17] Kim Y, Cho E, Park SJ, et al. One-pot microwave-assisted synthesis of reduced graphene oxide/nickel cobalt double hydroxide composites and their electrochemical behavior. J Ind Eng Chem, 2016, 33: 108-114.

[18] Meng X, Feng M, Zhang H, et al. Solvothermal synthesis of cobalt/nickel layered double hydroxides for energy storage devices. J Alloys Compd, 2017, 695: 3522-3529.

[19] Patel R, Inamdar AI, Hou B, et al. Solvothermal synthesis of high-performance Ni–Co layered double hydroxide nanofoam electrode for electrochemical energy storage. Curr Appl Phys, 2017, 17(4): 501-506.

[20] Wei W, Chen W, Ding L, et al. Construction of hierarchical three-dimensional interspersed flower-like nickel hydroxide for asymmetric supercapacitors. Nano Res, 2017, 10(11): 3726-3742.

[21] Shahrokhian S, Rahimi S, Mohammadi R. Nickel–cobalt layered double hydroxide ultrathin nanosheets coated on reduced graphene oxide nonosheets/nickel foam for high performance asymmetric supercapacitors. Int J Hydrogen Energy, 2018, 43(4): 2256-2267.

[22] Cai X, Shen X, Ma L, et al. Solvothermal synthesis of NiCo-layered double hydroxide nanosheets decorated on RGO sheets for high performance supercapacitor. Chem Eng J, 2015, 268: 251-259.

[23] Wang M, Xue J, Zhang F, et al. Facile synthesis of nickel-cobalt double hydroxide nanosheets with high rate capability for application in supercapacitor. J Nanopart Res, 2015, 17(2): 106

[24] Sun X, Wang G, Sun H, et al. Morphology controlled high performance supercapacitor behaviour of the Ni–Co binary hydroxide system. J Power Sources, 2013, 238: 150-156.

[25] Zhang C, Geng X, Tang S, et al. NiCo₂O₄@ rGO hybrid nanostructures on Ni foam as high-performance supercapacitor electrodes. J Mater Chem A, 2017, 5(12): 5912-5919.

[26] Wang B, Wang G, Wang H. Synthesis and electrochemical investigation of hollow hierarchical metal oxide microspheres for high performance lithium-ion batteries. Electrochim Acta, 2015, 156: 1-10.

[27] Zhao Y, Ran W, He J, et al. High-performance asymmetric supercapacitors based on multilayer MnO₂/graphene oxide nanoflakes and hierarchical porous carbon with enhanced cycling stability. Small, 2015, 11(11): 1310-1319.

[28] Han E, Han Y, Zhu L, et al. Polyvinyl pyrrolidone-assisted synthesis of flower-like nickel-cobalt layered double hydroxide on Ni foam for high-performance hybrid supercapacitor. Ionics, 2017

[29] Qi J, Chang Y, Sui Y, et al. Facile construction of 3D reduced graphene oxide wrapped Ni₃S₂ nanoparticles on Ni foam for high-performance asymmetric supercapacitor electrodes. Part Part Syst Charact, 2017, 34(12): 1700196

[30] Chen Z, Qin Y, Weng D, et al. Design and synthesis of hierarchical nanowire composites for electrochemical energy storage. Adv Funct Mater, 2009, 19(21): 3420-3426.

[31] Kovtyukhova NI, Ollivier PJ, Martin BR, et al. Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem Mater, 1999, 11(3): 771-778.

[32] Wang L, Lin C, Huang D, et al. A comparative study of composition and morphology effect of Ni_(x)Co_(1−x)(OH)₂ on oxygen evolution/reduction reaction. ACS Appl Mater Interfaces, 2014, 6(13): 10172-10180.

[33] Chen S, Duan J, Jaroniec M, et al. Three-dimensional n-doped graphene hydrogel/NiCo double hydroxide electrocatalysts for highly efficient oxygen evolution. Angew Chem, 2013, 52(51): 13567-13570.

[34] Ezhov BB, Malandin OG. Structure modification and change of electrochemical activity of nickel hydroxides. J Electrochem Soc, 1991, 138(4): 885-889.

[35] Min S, Zhao C, Zhang Z, et al. Synthesis of Ni(OH)₂/RGO pseudocomposite on nickel foam for supercapacitors with superior performance. J Mater Chem A, 2015, 3(7): 3641-3650.

[36] Jaubertie C, Holgado MJ, Román MSS, et al. Structural characterization and delamination of lactate-intercalated Zn, Al-layered double hydroxides. Chem Mater, 2006, 18(13): 3114-3121.

[37] Zhang Y, Cui B, Zhao C, et al. Co–Ni layered double hydroxides for water oxidation in neutral electrolyte. Phys Chem Chem Phys, 2013, 15(19): 7363-7369.

[38] Kamath PV, Ganguly S. Infrared spectroscopic studies of the oxide-hydroxides of Ni, Co and Mn. Mater Lett, 1991, 10(11–12): 537-539.

[39] Kosova NV, Devyatkina ET, Kaichev VV. Mixed layered Ni–Mn–Co hydroxides: crystal structure, electronic state of ions, and thermal decomposition. J Power Sources, 2007, 174(2): 735-740.

[40] Vincent Crist B. BE lookup table for signals from elements and common chemical species. Handbook of the elements and native oxides, 1999, Kawasaki, Japan: XPS International, Inc.

[41] Bai X, Li Q, Zhang H, et al. Nickel–cobalt layered double hydroxide nanowires on three dimensional graphene nickel foam for high performance asymmetric supercapacitors. Electrochim Acta, 2016, 215: 492-499.

[42] Zhang F, Yuan C, Lu X, et al. Facile growth of mesoporous Co₃O₄ nanowire arrays on Ni foam for high performance electrochemical capacitors. J Power Sources, 2012, 203: 250-256.

[43] Nguyen VH, Shim JJ. Three-dimensional nickel foam/graphene/NiCo₂O₄ as high-performance electrodes for supercapacitors. J Power Sources, 2015, 273: 110-117.

[44] Gao Y, Mi L, Wei W, et al. Double metal ions synergistic effect in hierarchical multiple sulfide microflowers for enhanced supercapacitor performance. ACS Appl Mater Interfaces, 2015, 7(7): 4311-4319.