A two-step approach to synthesis of Co(OH)₂/γ-NiOOH/reduced graphene oxide nanocomposite for high performance supercapacitors

Abstract

A two-step approach was reported to fabricate cobaltous hydroxide/γ-nickel oxide hydroxide/reduced graphene oxide (Co(OH)₂/γ-NiOOH/RGO) nanocomposites on nickel foam by combining the reduction of graphene oxide with the help of reflux condensation and the subsequent hydrothermal of Co(OH)₂ on RGO. The microstructural, surface morphology and electrochemical properties of the Co(OH)₂/γ-NiOOH/RGO nanocomposite were investigated. The results showed that the surface of the first-step fabricated γ-NiOOH/RGO nanocomposites was uniformly coated by Co(OH)₂ nanoflakes with lateral size of tens of nm and thickness of several nm. Co(OH)₂/γ-NiOOH/RGO nanocomposite demonstrated a high specific capacitance (745 mF/cm² at 0.5 mA/cm²) and a cycling stability of 69.8% after 1000 cycles at 30 mV/cm². γ-NiOOH/RGO//Co(OH)₂/γ-NiOOH/RGO asymmetric supercapacitor was assembled, and maximum gravimetric energy density of 57.3 W∙h/kg and power density of 66.1 kW/kg were achieved. The synergistic effect between the highly conductive graphene and the nanoflake Co(OH)₂ structure was responsible for the high electrochemical performance of the hybrid electrode. It is expected that this research could offer a simple method to prepare graphene-based electrode materials.

Keywords

reflux condensation / graphene / cobaltous hydroxide / supercapacitor

References

[1] Shao Y, El-Kady M F, Wang L J, . Graphene-based materials for flexible supercapacitors. Chemical Society Reviews, 2015, 44(11): 3639–3665

[2] Beidaghi M, Gogotsi Y. Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors. Energy & Environmental Science, 2014, 7(3): 867–884

[3] Jiang H, Lee P S, Li C. 3D carbon based nanostructures for advanced supercapacitors. Energy & Environmental Science, 2013, 6(1): 41–53

[4] Zhang W, Xu C, Ma C, . Nitrogen-superdoped 3D graphene networks for high-performance supercapacitors. Advanced Materials, 2017, 29(36): 1701677doi:10.1002/adma.201701677

[5] Wang C, Qu H, Peng T, . Large scale α-Co(OH)₂ needle arrays grown on carbon nanotube foams as free standing electrodes for supercapacitors. Electrochimica Acta, 2016, 191: 133–141

[6] Cheng J, Zhao B, Zhang W, . High-performance supercapacitor applications of NiO-nanoparticle-decorated millimeter-long vertically aligned carbon nanotube arrays via an effective supercritical CO₂-assisted method. Advanced Functional Materials, 2015, 25(47): 7381–7391

[7] Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors. Chemical Society Reviews, 2012, 41(2): 797–828

[8] El-Kady M F, Strong V, Dubin S, . Laser scribing of high-performance and flexible graphene-based electrochemical capacitors. Science, 2012, 335(6074): 1326–1330

[9] Zhao C, Ren F, Xue X, . A high-performance asymmetric supercapacitor based on Co(OH)₂/graphene and activated carbon electrodes. Journal of Electroanalytical Chemistry, 2016, 782: 98–102

[10] Choi N S, Chen Z, Freunberger S A, . Challenges facing lithium batteries and electrical double-layer capacitors. Angewandte Chemie International Edition, 2012, 51(40): 9994–10024

[11] Xing W, Qiao S, Ding R, . Superior electric double layer capacitors using ordered mesoporous carbons. Carbon, 2006, 44(2): 216–224

[12] Qiu Y, Zhao Y, Yang X, . Three-dimensional metal/oxide nanocone arrays for high-performance electrochemical pseudocapacitors. Nanoscale, 2014, 6(7): 3626–3631

[13] Tang Z, Tang C, Gong H. A high energy density asymmetric supercapacitor from nano-architectured Ni(OH)₂/carbon nanotube electrodes. Advanced Functional Materials, 2012, 22(6): 1272–1278

[14] Zhao C, Ren F, Xue X, . A high-performance asymmetric supercapacitor based on Co(OH)₂/graphene and activated carbon electrodes. Journal of Electroanalytical Chemistry, 2016, 782: 98–102

[15] Fan Z, Yan J, Wei T, . Asymmetric supercapacitors based on graphene/MnO₂ and activated carbon nanofiber electrodes with high power and energy density. Advanced Functional Materials, 2011, 21(12): 2366–2375

[16] Qu Q, Li L, Tian S, . A cheap asymmetric supercapacitor with high energy at high power: Activated carbon//K_0.27MnO₂·0.6H₂O. Journal of Power Sources, 2010, 195(9): 2789–2794

[17] Qu Q, Shi Y, Tian S, . A new cheap asymmetric aqueous supercapacitor: Activated carbon//NaMnO₂. Journal of Power Sources, 2009, 194(2): 1222–1225

[18] Yin T, Zhang W, Yin Y, . Co(OH)₂ nanoflakes grown on 3D graphene foam as a binder-free hybrid electrode for high-performance supercapacitors. Journal of Materials Science Materials in Electronics, 2017, 28(11): 7884–7891

[19] Wu S, Chen W, Yan L. Fabrication of a 3D MnO₂/graphene hydrogel for high-performance asymmetric supercapacitors. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(8): 2765–2772

[20] Chang J K, Wu C M, Sun I W. Nano-architectured Co(OH)₂ electrodes constructed using an easily-manipulated electrochemical protocol for high-performance energy storage applications. Journal of Materials Chemistry, 2010, 20(18): 3729–3735

[21] Wen J, Li S, Chen T, . Three-dimensional hierarchical NiCo hydroxide@Ni₃S₂ nanorod hybrid structure as high performance positive material for asymmetric supercapacitor. Electrochimica Acta, 2016, 222: 965–975

[22] Gao Z H, Zhang H, Cao G P, . Spherical porous VN and NiO_x as electrode materials for asymmetric supercapacitor. Electrochimica Acta, 2013, 87: 375–380

[23] Della Noce R, Eugénio S, Silva T, . α-Co(OH)₂/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium. Journal of Power Sources, 2015, 288: 234–242

[24] He Y S, Bai D W, Yang X, . A Co(OH)₂‒graphene nanosheets composite as a high performance anode material for rechargeable lithium batteries. Electrochemistry Communications, 2010, 12(4): 570–573

[25] Hu C C, Chen J C, Chang K H. Cathodic deposition of Ni(OH)₂ and Co(OH)₂ for asymmetric supercapacitors: Importance of the electrochemical reversibility of redox couples. Journal of Power Sources, 2013, 221: 128–133

[26] Chen Z, Ren W, Gao L, . Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nature Materials, 2011, 10(6): 424–428

[27] Wu Z S, Sun Y, Tan Y Z, . Three-dimensional graphene-based macro- and mesoporous frameworks for high-performance electrochemical capacitive energy storage. Journal of the American Chemical Society, 2012, 134(48): 19532–19535

[28] Jiang C, Zhao B, Cheng J, . Hydrothermal synthesis of Ni(OH)₂ nanoflakes on 3D graphene foam for high-performance supercapacitors. Electrochimica Acta, 2015, 173: 399–407

[29] Hofmann U, Frenzel A. Die Reduktion von Graphitoxyd mit Schwefelwasserstoff. Kolloid Zeitschrift, 1934, 68(2): 149–151in German)

[30] Gao W, Alemany L B, Ci L, . New insights into the structure and reduction of graphite oxide. Nature Chemistry, 2009, 1(5): 403–408

[31] Si Y, Samulski E T. Synthesis of water soluble graphene. Nano Letters, 2008, 8(6): 1679–1682

[32] Stankovich S, Dikin D A, Piner R D, . Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon, 2007, 45(7): 1558–1565

[33] Fan Z, Wang K, Wei T, . An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder. Carbon, 2010, 48(5): 1686–1689

[34] Li Z, Fan G, Tan Z, . Uniform dispersion of graphene oxide in aluminum powder by direct electrostatic adsorption for fabrication of graphene/aluminum composites. Nanotechnology, 2014, 25(32): 325601

[35] Liu Q Y, He M, Xu X J, . Self-assembly of graphene oxide on the surface of aluminum foil. New Journal of Chemistry, 2013, 37(1): 181–187

[36] Liu Y, Li Y, Zhong M, . A green and ultrafast approach to the synthesis of scalable graphene nanosheets with Zn powder for electrochemical energy storage. Journal of Materials Chemistry, 2011, 21(39): 15449–15455 doi:10.1039/C1JM12599K

[37] Compton O C, Jain B, Dikin D A, . Chemically active reduced graphene oxide with tunable C/O ratios. ACS Nano, 2011, 5(6): 4380–4391

[38] Xu F, Deng M, Li G, . Electrochemical behavior of cuprous oxide–reduced graphene oxide nanocomposites and their application in nonenzymatic hydrogen peroxide sensing. Electrochimica Acta, 2013, 88: 59–65

[39] Jiang J, Liu J, Ding R, . Large-scale uniform α-Co(OH)₂ long nanowire arrays grown on graphite as pseudocapacitor electrodes. ACS Applied Materials & Interfaces, 2011, 3(1): 99–103

[40] Chang L, Ren F, Zhao C, . Synthesis of Co(OH)₂/Ni(OH)₂ nanomaterials with excellent pseudocapacitive behavior and high cycling stability for supercapacitors. Journal of Electroanalytical Chemistry, 2016, 778: 110–115

[41] Ping Y, Yan J M, Wang Z L, . Ag_0.1‒Pd_0.9/rGO: an efficient catalyst for hydrogen generation from formic acid/sodium formate. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2013, 1(39): 12188–12191

[42] Zhao C, Wang X, Wang S, . Synthesis of Co(OH)₂/graphene/Ni foam nano-electrodes with excellent pseudocapacitive behavior and high cycling stability for supercapacitors. International Journal of Hydrogen Energy, 2012, 37(16): 11846–11852

[43] Zhao C, Wang X, Wang S, . Pseudocapacitive properties of cobalt hydroxide electrodeposited on Ni-foam-supported carbon nanomaterial. Materials Research Bulletin, 2013, 48(9): 3189–3195

[44] Pang H, Yan Z, Wang W, . Facile fabrication of NH₄CoPO₄·H₂O nano/microstructures and their primarily application as electrochemical supercapacitor. Nanoscale, 2012, 4(19): 5946–5953

[45] Wu M S, Guo Z S, Jow J J. Highly regulated electrodeposition of needle-like manganese oxide nanofibers on carbon fiber fabric for electrochemical capacitors. The Journal of Physical Chemistry C, 2010, 114(49): 21861–21867

[46] Wang C, Xu J, Yuen M F, . Hierarchical composite electrodes of nickel oxide nanoflake 3D graphene for high-performance pseudocapacitors. Advanced Functional Materials, 2014, 24(40): 6372–6380

[47] Huang Z, Zhao X, Ren J, . Electrochemical deposition of nanostructured manganese oxide on carbon cloth for flexible high-performance supercapacitor electrodes. Journal of Nanoscience and Nanotechnology, 2016, 16(6): 5668–5675

[48] Jeong K H, Lee H J, Simpson M F, . Electrochemical synthesis of graphene/MnO₂ nano-composite for application to supercapacitor electrode. Journal of Nanoscience and Nanotechnology, 2016, 16(5): 4620–4625

[49] Lu X F, Wu D J, Li R Z, . Hierarchical NiCo₂O₄ nanosheets@hollow microrod arrays for high-performance asymmetric supercapacitors. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(13): 4706–4713

[50] Chang J, Xu H, Sun J, . High pseudocapacitance material prepared via in situ growth of Ni(OH)₂ nanoflakes on reduced graphene oxide. Journal of Materials Chemistry, 2012, 22(22): 11146–11150

[51] Wang Y M, Zhang X, Guo C Y, . Controllable synthesis of 3D Ni_xCo_1−x oxides with different morphologies for high-capacity supercapacitors. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2013, 1(42): 13290–13300

[52] Ji J, Zhang L L, Ji H, . Nanoporous Ni(OH)₂ thin film on 3D ultrathin-graphite foam for asymmetric supercapacitor. ACS Nano, 2013, 7(7): 6237–6243

[53] Yan J, Fan Z, Sun W, . Advanced asymmetric supercapacitors based on Ni(OH)₂/graphene and porous graphene electrodes with high energy density. Advanced Functional Materials, 2012, 22(12): 2632–2641

[54] Li M, Xu S, Cherry C, . Asymmetrical supercapacitor composed of thin Co(OH)₂ nanoflakes on three-dimensional Ni/Si microchannel plates with superior electrochemical performance. Electrochimica Acta, 2014, 149: 18–27

[55] Fan L Q, Liu G J, Wu J H, . Asymmetric supercapacitor based on graphene oxide/polypyrrole composite and activated carbon electrodes. Electrochimica Acta, 2014, 137: 26–33

[56] Jiang Y, Chen L, Zhang H, . Two-dimensional Co₃O₄ thin sheets assembled by 3D interconnected nanoflake array framework structures with enhanced supercapacitor performance derived from coordination complexes. Chemical Engineering Journal, 2016, 292: 1–12

[57] Fu G, Ma L, Gan M, . Fabrication of 3D spongia-shaped polyaniline/MoS₂ nanospheres composite assisted by polyvinylpyrrolidone (PVP) for high-performance supercapacitors. Synthetic Metals, 2017, 224: 36–45

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 51605293 and 51702213) and the Natural Science Foundation of Shanghai (16ZR1423500). The authors also acknowledge financial support from the Program for Associate Professor of Special Appointment (Young Eastern Scholar) at Shanghai Institutions of Higher Learning (QD2016013).

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