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Effect of templating agent on Ni, Co, Al-based layered double hydroxides for high-performance asymmetric supercapacitors

  • Yahong Tian
  • Lingzhi ZhuEmail author
  • Enshan Han
  • Mei Shang
  • Mengchao Song
Original Paper


Transition metal layered double hydroxides (LDHs) are one of the great potential electrode materials for pseudocapacitors. In this paper, NiCo-LDHs, NiAl-LDHs, CoAl-LDHs, and NiCoAl-LDHs were synthesized by hydrothermal method and these materials directly grew on foamed nickel. The electrochemical performance of these materials was investigated by galvanostatic charge-discharge test (GCD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The morphology and physicochemical properties of the materials were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The capacity of these materials at 1 A g−1 was 894.4, 942.4, 885, and 1068 F g−1, respectively. The capacity retention rates after 2000 cycles at 10 A g−1 were 80.05%, 76.4%, 81.92%, and 83.7%, respectively. And then, we synthesized NiCoAl-LDHs with 0.002, 0.003, 0.004, and 0.005 mol Tween80 by the same experimental method. The influence on the morphology and electrochemical properties of NiCoAl-LDHs with different dosage of template agents was investigated. The results show that the capacity at 1 A g−1 was 1336.4, 1433.2, 1430, and 1289.2 F g−1, respectively. The capacity retention rates after 2000 cycles at 10 A g−1 were 85%, 92%, 90%, and 88%, respectively. An asymmetric supercapacitor (ASC) was assembled with 0.003 mol Tween80 as positive electrode and activated carbon as negative electrode. The ASC device exhibited an ultra-high energy density of 89.79 Wh kg−1 at power density of 775 W kg−1 as well as long-term stability (86.02% of its initial capacitance retention at 10 A g−1over 2000 cycles), outperforming most of LDH and metal oxides ASCs.


NiCoAl-LDHs Layered double hydroxide Tween80 Asymmetric supercapacitor 



The authors appreciate the contributions of the reviewers in ensuring the quality of the paper is improved. The authors would also like to thank Dr. Enshan Han in Hebei University of Technology at Tianjin for his support.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Simon P, Gogotsi Y (2008) Materials for electrochemical capacitors. Nat Mater 7:845–854CrossRefPubMedPubMedCentralGoogle Scholar
  2. 2.
    Fang J, Li M, Li Q, Zhang W, Shou Q, Liu F, Zhang X (2012) Microwave-assisted synthesis of CoAl-layered double hydroxide/graphene oxide composite and its application insupercapacitors. Electrochim Acta 85:248–255CrossRefGoogle Scholar
  3. 3.
    Liu SD, Hui KS, Hui KN (2015) 1D hierarchical MnCo2O4 nanowire@MnO2 sheet core-shell arrays on graphite paper as superior electrodes for asymmetric supercapacitors. ChemNanoMat 1(8):593–602CrossRefGoogle Scholar
  4. 4.
    Zhang LJ, Hui KN, Hui KS, Lee H (2016) High-performance hybrid supercapacitor with 3D hierarchical porous flower-like layered double hydroxide grown on nickel foam as binder-free electrode. J Power Sources 318:76–85CrossRefGoogle Scholar
  5. 5.
    Mai L, Tian X, Xu X, Chang L, Xu L (2016) Nanowire electrodes for electrochemical energy storage devices. Chem Rev 114:11828–11862CrossRefGoogle Scholar
  6. 6.
    Chen H, Hu L, Chen M, Yan Y, Wu L (2014) Nickel-cobalt layered double hydroxide nanosheets for high-performance supercapacitor electrode materials. Adv Funct Mater 24(7):934–942CrossRefGoogle Scholar
  7. 7.
    Forticaux A, Dang L, Liang H, Jin S (2015) Controlled synthesis of layered double hydroxide nanoplates driven by screw dislocations. Nano Lett 15(5):3403–3409CrossRefPubMedGoogle Scholar
  8. 8.
    Xu MW, Zhao DD, Bao SJ et al (2007) Mesoporous amorphous MnO2, as electrode material for supercapacitor. J Solid State Electrochem 11(8):1101–1107CrossRefGoogle Scholar
  9. 9.
    Seftel EM, Niarchos M, Vordos N, Nolan JW, Mertens M, Mitropoulos AC, Vansant EF, Cool P (2015) LDH and TiO2/ LDH-type nanocomposite systems: a systematic study on structural characteristics. Microporous Mesoporous Mater 203:208–215CrossRefGoogle Scholar
  10. 10.
    Liu CJ, Chen SJ, Li YW et al (2012) Synthesis and electrochemical performance of alpha-nickel hydroxide codoped with Al3+ and Ca2+. Ionics 18:197–202CrossRefGoogle Scholar
  11. 11.
    Vighnesha KM, Shruthi S et al (2018) Synthesis and characterization of activated carbon/conducting polymer composite electrode for supercapacitor applications. J Mater Sci Mater Electron 22:1–8Google Scholar
  12. 12.
    Han ES, Han YJ, Zhu LZ et al (2018) Polyvinyl pyrrolidone-assisted synthesis of flower-like nickel-cobalt layered double hydroxide on Ni foam for high-performance hybrid supercapacitor. Ionics 24:2705–2715CrossRefGoogle Scholar
  13. 13.
    Li L, Hui KS, Hui KN et al (2017) Ultrathin petal-like NiAl layered double oxide/sulfide composites as an advanced electrode for high-performance asymmetric supercapacitors. J Mater Chem A 5(37):19687–19696CrossRefGoogle Scholar
  14. 14.
    Zhi M, Xiang C, Li J, Li M, Wu N (2013) Nanostructured carbon–metal oxide composite electrodes for supercapacitors: a review. Nanoscale 5:72–88CrossRefPubMedGoogle Scholar
  15. 15.
    Wang G, Zhang L, Zhang J (2012) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41:797–828CrossRefPubMedGoogle Scholar
  16. 16.
    Lu Z, Zhu W, Lei X, Williams GR, O’Hare D, Chang Z, Sun X, Duan X (2012) High pseudocapacitive cobalt carbonate hydroxide films derived from CoAl layered double hydroxides. Nanoscale 4:3640–3643CrossRefPubMedGoogle Scholar
  17. 17.
    Wang B, Williams GR, Chang Z, Jiang M, Liu J, Lei X, Sun X (2014) Hierarchical NiAl layered double hydroxide/multiwalled carbon nanotube/nickel foam electrodes with excellent pseudocapacitive properties. ACS Appl Mater Interfaces 6:16304–16311CrossRefPubMedGoogle Scholar
  18. 18.
    Zhao J, Chen J, Xu S, Shao M, Zhang Q, Wei F, Ma J, Wei M, Evans DG, Duan X (2014) Hierarchical NiMn layered double hydroxide/carbon nanotubes architecture with superb energy density for flexible supercapacitors. Adv Funct Mater 24:2938–2946CrossRefGoogle Scholar
  19. 19.
    Cheng Y, Zhang H, Varanasi CV, Liu J (2013) Improving the performance of cobalt–nickel hydroxide-based self-supporting electrodes for supercapacitors using accumulative approaches. Energy Environ Sci 6:3314–3321CrossRefGoogle Scholar
  20. 20.
    Liu XM, Zhang YH, Zhang XG, Fu SY (2014) Studies on Me/Al-layered double hydroxides (Me=Ni and Co) as electrode materials for electrochemical capacitors. Electrochim Acta 49:3137–3141CrossRefGoogle Scholar
  21. 21.
    Gupta V, Gupta S, Miura N (2009) Electrochemically synthesized large area network of CoxNiyAlz layered triple hydroxides nanosheets: a high performance supercapacitor. J Power Sources 189:1292–1295CrossRefGoogle Scholar
  22. 22.
    Liu F, Chen YY, Liu Y et al (2019) Integrating ultrathin and modified NiCoAl-layered double hydroxide nanosheets with N-doped reduced graphene oxide for high-performance all-solid-state supercapacitors. Nanoscale 11:9896–9905CrossRefPubMedGoogle Scholar
  23. 23.
    Xiao YH, Su DC, Wang XZ et al (2017) Ultrahigh energy density and stable supercapacitor with 2D NiCoAl layered double hydroxide. Electrochim Acta 253:324–332CrossRefGoogle Scholar
  24. 24.
    He XY, Liu Q, Liu JY et al (2017) Hierarchical NiCo2O4@NiCoAl-layered double hydroxide core/shell nanoforest arrays as advanced electrodes for high-performance asymmetric supercapacitors. Alloys Compd 724:130–138CrossRefGoogle Scholar
  25. 25.
    Yang J, Yu C, Fan XM, et al (2013) Facile fabrication of MWCNT-doped NiCoAl-layered double hydroxide nanosheets with enhanced electrochemical performances†. J Mater Chem A 1: 1963–1968.Google Scholar
  26. 26.
    Zhao J, Chen J, Xu S, Shao M, Yan D, Wei M, Evans DG, Duan X (2013) CoMn-layered double hydroxide nanowalls supported on carbon fibers for high-performance flexible energy storage devices. J Mater Chem A 1(31):8836CrossRefGoogle Scholar
  27. 27.
    Qiao YQ, Jia P, Zhang XY et al (2017) One-pot synthesized mesoporous Ni-Co hydroxide for high performance supercapacitors. Ionics 23:1229–1238CrossRefGoogle Scholar
  28. 28.
    Mondal AK, Su D, Chen S, Sun B, Li K, Wang G (2014) A simple approach to prepare nickel hydroxide nanosheets for enhanced pseudocapacitive performance. RSC Adv 4(37):19476–19481CrossRefGoogle Scholar
  29. 29.
    Dong XC, Xu H, Wang XW et al (2012) 3D graphene-cobalt oxide electrode for high-performance supercapacitor and enzymeless glucose detection. ACS Nano 6(4):3206–3213CrossRefPubMedGoogle Scholar
  30. 30.
    Shen L, Uchaker E, Zhang X et al (2012) Hydrogenated Li(4)Ti(5)O(12) nanowire arrays for high rate lithium ion batteries. Adv Mater 24(48):6502–6506CrossRefPubMedGoogle Scholar
  31. 31.
    Lin Z, Yan X, Lang J et al (2015) Adjusting electrode initial potential to obtain high-performance asymmetric supercapacitor based on porous vanadium pentoxide nanotubes and activated carbon nanorods. J Power Sources 279:358–364CrossRefGoogle Scholar
  32. 32.
    Xu Y, Wang L, Cao P et al (2016) Mesoporous composite nickel cobalt oxide/graphene oxide synthesized via a template-assistant co-precipitation route as electrode material for supercapacitors. J Power Sources 306:742–752CrossRefGoogle Scholar
  33. 33.
    Yan L, Kong H, Li ZJ (2013) Preparation and supercapacitive properties of 3D graphene/nickel aluminum layered double metal hydroxide. Acta Chim Sin 71(5):822–828CrossRefGoogle Scholar
  34. 34.
    Gao Z, Yang W, Wang J et al (2015) Flexible all-solid-state hierarchical NiCo2O4/porous graphene paper asymmetric supercapacitors with an exceptional combination of electrochemical properties. Nano Energy 13:306–317CrossRefGoogle Scholar
  35. 35.
    Salunkhe RR, Jang K, Yu H et al (2011) Chemical synthesis and electrochemical analysis of nickel cobaltite nanostructures for supercapacitor applications. J Alloys Compd 509(23):6677–6682CrossRefGoogle Scholar
  36. 36.
    Liu C, Jiang W, Hu F et al (2018) Mesoporous NiCo2O4 nanoneedle arrays as supercapacitor electrode materials with excellent cycling stabilities. Inorg Chem Front 5(4):835–843CrossRefGoogle Scholar
  37. 37.
    Zeng ZZ, Zhu LZ, Han ES et al (2019) Soft-templating and hydrothermal synthesis of NiCo2O4 nanomaterials on Ni foam for high-performance. Ionics 25:2791–2803CrossRefGoogle Scholar
  38. 38.
    Xia QX, Hui KS, Hui KN et al (2015) Facile synthesis of manganese carbonate quantum dots/Ni(HCO3)(2)-MnCO3 composites as advanced cathode materials for high energy density asymmetric supercapacitors. J Mater Chem A 3(44):22102–22117CrossRefGoogle Scholar
  39. 39.
    Zhang L, Ou M, Yao H, Li Z, Qu D, Liu F, Wang J, Wang J, Li Z (2015) Enhanced supercapacitive performance of graphite-like C3N4 assembled with NiAl-layered double hydroxide. Electrochim Acta 186:292–301CrossRefGoogle Scholar
  40. 40.
    Tomboc GM, Jadhav HS, Kim H (2017) PVP assisted morphologycontrolled synthesis of hierarchical mesoporous ZnCo2O4 nanoparticles for high-performance pseudocapacitor. Chem Eng J 308:202–213CrossRefGoogle Scholar
  41. 41.
    Zhu Y, Wang J, Wu Z et al (2015) An electrochemical exploration of hollow NiCo2O4 submicrospheres and its capacitive performances. J Power Sources 287(ISSN):307–315CrossRefGoogle Scholar
  42. 42.
    Zhao Y, He X, Chen R et al (2018) A flexible all-solid-state asymmetric supercapacitors based on hierarchical carbon cloth@CoMoO4@NiCo layered double hydroxide core-shell heterostructures. Chem Eng J 352:29–38CrossRefGoogle Scholar
  43. 43.
    Ye P, Dong H, Xu Y, Zhao C, Liu D (2018) NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro−/nano-spheres as cathode material for high-performance lithium ion battery. Appl Surf Sci 428:469–477CrossRefGoogle Scholar
  44. 44.
    Ghodbane O, Louro M, Coustan L et al (2013) Microstructural and morphological effects on charge storage properties in MnO2-carbon nanofibers based supercapacitors. J Electrochem Soc 160(11):A2315–A2321CrossRefGoogle Scholar
  45. 45.
    Li YH, Wu XW et al (2018) Fabrication of urchin-like NiCo2O4 microspheres assembled by using SDS as soft template for anode materials of Lithium-ion batteries. Ionics 24:1329–1337CrossRefGoogle Scholar
  46. 46.
    Bai Y, Liu MM, Sun J et al (2016) Fabrication of Ni-Co binary oxide/reduced graphene oxide composite with high capacitance and cyclicity as efficient electrode for supercapacitors. Ionics 22:535–544CrossRefGoogle Scholar
  47. 47.
    Meher SK, Justin P, Rao GR (2011) Microwave-mediatedsynthesis for improved morphology and pseudocapacitance performance of nickel oxide. ACS Appl Mater Interfaces 3(6):2063–2073CrossRefPubMedGoogle Scholar
  48. 48.
    Bai X, Liu Q, Liu JY et al (2019) All-solid state asymmetric supercapacitor based on NiCoAl layered double hydroxide nanopetals on robust 3D graphene and modified mesoporous carbon. Chem Eng J 328:873–883CrossRefGoogle Scholar
  49. 49.
    Zhang LL, Zhao S, Tian XN et al (2010) Layered graphene oxide nanostructures with sandwiched conducting polymers as supercapacitor electrodes. Langmuir ACS J Surf Colloids 26(22):17624–17628CrossRefGoogle Scholar
  50. 50.
    Liu ZQ, Chen GF, Zhou PL, Li N, Su YZ (2016) Building layered NixCo2x(OH)6x nanosheets decorated three-dimensional Ni frameworks for electrochemical applications. J Power Sources 317:1–9CrossRefGoogle Scholar
  51. 51.
    Zhu W, Lu Z, Zhang G et al (2013) Hierarchical Ni0.25Co0.75(OH)2 nanoarrays for a high-performance supercapacitor electrode prepared by an in situ conversion process. J Mater Chem A 1(29):8327–8331CrossRefGoogle Scholar
  52. 52.
    Liu S, Hui KS, Hui KN (2016) Vertically stacked bilayer CuCo2O4/MnCO2O4 heterostructures on functionalized graphite paper for high-performance electrochemical capacitors. J Mater Chem A 4(21):8061–8071CrossRefGoogle Scholar
  53. 53.
    Yang J, Yu C, Fan X (2014) 3D architecture materials made of NiCoAl-LDH nanoplates coupled with NiCo-carbonate hydroxide nanowires grown on flexible graphite paper for asymmetric supercapacitors. Adv Energy Mater 4:1–8Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yahong Tian
    • 1
  • Lingzhi Zhu
    • 1
    Email author
  • Enshan Han
    • 1
  • Mei Shang
    • 1
  • Mengchao Song
    • 2
  1. 1.School of Chemical Engineering and TechnologyHebei University of TechnologyTianjinPeople’s Republic of China
  2. 2.School of Materials Science and EngineeringHebei University of TechnologyTianjinPeople’s Republic of China

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