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Ionics

, Volume 25, Issue 9, pp 4409–4423 | Cite as

Influence of thiourea concentration on the CuS nanostructures and identification of the most suited electrolyte for high energy density supercapacitor

  • Nandhini Sonai Muthu
  • Shobana Devi Samikannu
  • Muralidharan GopalanEmail author
Original Paper
  • 62 Downloads

Abstract

The energy density of a supercapacitor is largely reliant on functional parameters of electrode material and electrolyte. To improve the energy density of the CuS asymmetric device, optimization of sulfur concentration (thiourea) in the precursor and identification of the most suited electrolyte have been attempted. The changes in thiourea concentration greatly affect the physical and electrochemical features of CuS. The highest specific capacitance of 298 F g−1 at 2 A g−1 was obtained for copper sulfide nanoparticles prepared with 1:2 ratio of copper acetate and thiourea (C3). It exhibits excellent cycling stability in 2 M KOH electrolyte. In addition, to evaluate the most suited electrolyte, electrochemical studies were performed with different electrolytes (H2SO4, Na2SO4, KOH and LiClO4 in propylene carbonate). Based on the electrochemical results, it was found that an outstanding performance has originated from H2SO4 electrolyte (773 F g−1 at 2 A g−1). The C3 electrode exhibits no perceptible degradation in capacity even after 4000 charge-discharge cycles in acidic electrolyte. Further, for real-life applications, an asymmetric device was fabricated using C3 as a cathode and PVA/ H2SO4 as electrolyte. The device attained a highest energy density of 21 W h kg−1 at a power density of 310 W kg−1. Furthermore, lighting up of red and yellow LEDs is demonstrated using the fabricated asymmetric device. The efficient device performances concluded that C3 is a potential cathode material for future supercapacitor applications.

Graphical abstract

Keywords

Copper sulfide Hydrothermal method Various electrolytes Cyclic voltammetry Specific capacitance 

Notes

Funding information

One of the authors, S. Nandhini (RGNF-2015-17-SC-TAM-18395), is thankful to the University Grants Commission, New Delhi for providing the financial support through Rajiv Gandhi National Fellowship (RGNF).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Wilde G (ed) (2009) Nanostructured materials. Vol. 1. ElsevierGoogle Scholar
  2. 2.
    Lai CH, Huang KW, Cheng JH, Lee CY, Hwang BJ, Chen LJ (2010) Direct growth of high-rate capability and high capacity copper sulfide nanowire array cathodes for lithium-ion batteries. J Mater Chem 20(32):6638–6645Google Scholar
  3. 3.
    Lai CH, Lu MY, Chen LJ (2012) Metal sulfide nanostructures: synthesis, properties and applications in energy conversion and storage. J Mater Chem 22(1):19–30Google Scholar
  4. 4.
    Gao MR, Xu YF, Jiang J, Yu SH (2013) Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices. Chem Soc Rev 42(7):2986–3017Google Scholar
  5. 5.
    Gross S, Vittadini A, Dengo N (2017) Functionalisation of colloidal transition metal sulphides nanocrystals: a fascinating and challenging playground for the chemist. Crystals 7(4):110–150Google Scholar
  6. 6.
    Rui X, Tan H, Yan Q (2014) Nanostructured metal sulfides for energy storage. Nanoscale 6(17):9889–9924Google Scholar
  7. 7.
    Lide DR (1995) CRC handbook of chemistry and physics, 53rd edn. CRC Press, Boca RatonGoogle Scholar
  8. 8.
    Alsfasser R, Janiak C, Klapötke TM, Meyer HJ (2012) Moderne Anorganische Chemie, 4th edn. Walter de Gruyter, BerlinGoogle Scholar
  9. 9.
    Miller TM, Bederson B (1978) Atomic and molecular polarizabilities - a review of recent advances. Adv Atom Mol Phys 13:1–55Google Scholar
  10. 10.
    Huang KJ, Zhang JZ, Jia YL, Xing K, Liu YM (2015) Acetylene black incorporated layered copper sulfide nanosheets for high-performance supercapacitor. J Alloy Compd 641:119–126Google Scholar
  11. 11.
    Huang KJ, Zhang JZ, Fan Y (2015) One-step solvothermal synthesis of different morphologies CuS nanosheets compared as supercapacitor electrode materials. J Alloy Compd 625:158–163Google Scholar
  12. 12.
    Wang G, Zhang M, Lu L, Xu H, Xiao Z, Liu S, Gao S, Yu Z (2018) One-pot synthesis of CuS nanoflower-decorated active carbon layer for high-performance asymmetric supercapacitors. ChemNanoMat 4(9):964–971Google Scholar
  13. 13.
    Raj CJ, Kim BC, Cho WJ, Lee WG, Seo Y, Yu KH (2014) Electrochemical capacitor behavior of copper sulfide (CuS) nanoplatelets. J Alloy Compd 586:191–196Google Scholar
  14. 14.
    Wang Y, Liu F, Ji Y, Yang M, Liu W, Wang W, Sun Q, Zhang Z, Zhao X, Liu X (2015) Controllable synthesis of various kinds of copper sulfides (CuS, Cu7S4, Cu9S5) for high-performance supercapacitors. Dalton Trans 44(22):10431–10437Google Scholar
  15. 15.
    Peng H, Ma G, Sun K, Mu J, Wang H, Lei Z (2014) High-performance supercapacitor based on multi-structural CuS@polypyrrole composites prepared by in situ oxidative polymerization. J Mater Chem A 2(10):3303–3307Google Scholar
  16. 16.
    Durga IK, Rao SS, Reddy AE, Gopi CV, Kim HJ (2018) Achieving copper sulfide leaf like nanostructure electrode for high performance supercapacitor and quantum-dot sensitized solar cells. Appl Surf Sci 435:666–675Google Scholar
  17. 17.
    Mehare RS, Ranganath SP, Chaturvedi V, Badiger MV, Shelke MV (2017) In situ synthesis of nitrogen-and sulfur-enriched hierarchical porous carbon for high-performance supercapacitor. Energy Fuel 32(1):908–915Google Scholar
  18. 18.
    Li W, Bu Y, Jin H, Wang J, Zhang W, Wang S, Wang J (2013) The preparation of hierarchical flowerlike NiO/reduced graphene oxide composites for high performance supercapacitor applications. Energy Fuel 27(10):6304–6310Google Scholar
  19. 19.
    Minakshi M, Meyrick D, Appadoo D (2013) Maricite (NaMn1/3Ni1/3Co1/3PO4)/activated carbon: hybrid capacitor. Energy Fuel 27(6):3516–3522Google Scholar
  20. 20.
    Maheswari N, Muralidharan G (2015) Supercapacitor behavior of cerium oxide nanoparticles in neutral aqueous electrolytes. Energy Fuel 29(12):8246–8253Google Scholar
  21. 21.
    Zhong C, Deng Y, Hu W, Qiao J, Zhang L, Zhang J (2015) A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem Soc Rev 44(21):7484–7539Google Scholar
  22. 22.
    Tian L, Yuan A (2009) Electrochemical performance of nanostructured spinel LiMn2O4 in different aqueous electrolytes. J Power Sources 192(2):693–697Google Scholar
  23. 23.
    Wang G, Zhang L, Zhang J (2012) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41(2):797–828Google Scholar
  24. 24.
    Ramesan MT (2013) Synthesis, characterization, and conductivity studies of polypyrrole/copper sulfide nanocomposites. J Appl Polym Sci 128(3):1540–1546Google Scholar
  25. 25.
    Shan J, Pulkkinen P, Vainio U, Maijala J, Merta J, Jiang H, Serimaa R, Kauppinen E, Tenhu H (2008) Synthesis and characterization of copper sulfide nanocrystallites with low sintering temperatures. J Mater Chem 18(27):3200–3208Google Scholar
  26. 26.
    Podili S, Geetha D, Ramesh PS (2017) One-pot synthesis of CTAB stabilized mesoporous cobalt doped CuS nanoflower with enhanced pseudocapacitive behavior. J Mater Sci-Mater El 28(20):15387–15397Google Scholar
  27. 27.
    Du H, Liu D, Wu H, Xia W, Zhang X, Chen Z, Liu Y, Liu H (2016) Surface modification of nickel sulfide nanoparticles: towards stable ultra-dispersed nanocatalysts for residue hydrocracking. Chem Cat Chem 8(8):1543–1550Google Scholar
  28. 28.
    Yin PF, Han XY, Zhou C, Xia CH, Hu CL, Sun LL (2015) Large-scale synthesis of nickel sulfide micro/nanorods via a hydrothermal process. Int J Min Met Mater 22(7):762–769Google Scholar
  29. 29.
    Pandey G (2012) Synthesis, characterization and optical properties determination of millerite NiS nanorods. Phys E Low Dimens Syst Nanostruct 44(7–8):1657–1661Google Scholar
  30. 30.
    Nandhini SM, Muralidharan G (2019) Mesoporous nickel sulphide nanostructures for enhanced supercapacitor performance. Appl Surf Sci 480:186–198Google Scholar
  31. 31.
    Akinwolemiwa B, Peng C, Chen GZ (2015) Redox electrolytes in supercapacitors. J Electrochem Soc 162(5):A5054–A5059Google Scholar
  32. 32.
    Laheäär A, Przygocki P, Abbas Q, Béguin F (2015) Appropriate methods for evaluating the efficiency and capacitive behavior of different types of supercapacitors. Electrochem Commun 60:21–25Google Scholar
  33. 33.
    Nagamuthu S, Vijayakumar S, Muralidharan G (2013) Synthesis of Mn3O4/amorphous carbon nanoparticles as electrode material for high performance supercapacitor applications. Energy Fuel 27(6):3508–3515Google Scholar
  34. 34.
    Sudhan N, Subramani K, Karnan M, Ilayaraja N, Sathish M (2016) Biomass-derived activated porous carbon from rice straw for a high-energy symmetric supercapacitor in aqueous and non-aqueous electrolytes. Energy Fuel 31(1):977–985Google Scholar
  35. 35.
    Sankar KV, Kalpana D, Selvan RK (2012) Electrochemical properties of microwave-assisted reflux-synthesized Mn3O4 nanoparticles in different electrolytes for supercapacitor applications. J Appl Electrochem 42(7):463–470Google Scholar
  36. 36.
    Ray RS, Sarma B, Jurovitzki AL, Misra M (2015) Fabrication and characterization of titania nanotube/cobalt sulfide supercapacitor electrode in various electrolytes. Chem Eng J 260:671–683Google Scholar
  37. 37.
    Chen LM, Lai QY, Hao YJ, Zhao Y, Ji XY (2009) Investigations on capacitive properties of the AC/V2O5 hybrid supercapacitor in various aqueous electrolytes. J Alloy Compd 467(1–2):465–471Google Scholar
  38. 38.
    Niu L, Chen L, Zhang J, Jiang P, Liu Z (2018) Revisiting the open-framework zinc hexacyanoferrate: the role of ternary electrolyte and sodium-ion intercalation mechanism. J Power Sources 380:135–141Google Scholar
  39. 39.
    Tobishima SI, Arakawa M, Yamaki JI (1988) Electrolytic properties of LiClO4—propylene carbonate mixed with amide-solvents for lithium batteries. Electrochim Acta 33(2):239–244Google Scholar
  40. 40.
    Hsu YK, Chen YC, Lin YG (2014) Synthesis of copper sulfide nanowire arrays for high-performance supercapacitors. Electrochim Acta 139:401–407Google Scholar
  41. 41.
    Zhang J, Feng H, Yang J, Qin Q, Fan H, Wei C, Zheng W (2015) Solvothermal synthesis of three-dimensional hierarchical CuS microspheres from a cu-based ionic liquid precursor for high-performance asymmetric supercapacitors. ACS Appl Mater Interfaces 7(39):21735–21744Google Scholar
  42. 42.
    Zhu T, Xia B, Zhou L, Lou XWD (2012) Arrays of ultrafine CuS nanoneedles supported on a CNT backbone for application in supercapacitors. J Mater Chem 22(16):7851–7855Google Scholar
  43. 43.
    Xu W, Liang Y, Su Y, Zhu S, Cui Z, Yang X, Inoue A, Wei Q, Liang C (2016) Synthesis and properties of morphology controllable copper sulphide nanosheets for supercapacitor application. Electrochim Acta 211:891–899Google Scholar
  44. 44.
    Krishnamoorthy K, Veerasubramani GK, Rao AN, Kim SJ (2014) One-pot hydrothermal synthesis, characterization and electrochemical properties of CuS nanoparticles towards supercapacitor applications. Mater Res Express 1(3):035006Google Scholar
  45. 45.
    Peng H, Ma G, Mu J, Sun K, Lei Z (2014) Controllable synthesis of CuS with hierarchical structures via a surfactant-free method for high-performance supercapacitors. Mater Lett 122:25–28Google Scholar
  46. 46.
    Peng H, Wei C, Wang K, Meng T, Ma G, Lei Z, Gong X (2017) Ni0.85Se@ MoSe2 nanosheet arrays as the electrode for high-performance supercapacitors. ACS Appl Mater Interfaces 9(20):17067–17075Google Scholar
  47. 47.
    De B, Balamurugan J, Kim NH, Lee JH (2017) Enhanced electrochemical and photocatalytic performance of core–shell CuS @ carbon quantum dots @ carbon hollow nanospheres. ACS Appl Mater Interfaces 9(3):2459–2468Google Scholar
  48. 48.
    Fu W, Han W, Zha H, Mei J, Li Y, Zhang Z, Xie E (2016) Nanostructured CuS networks composed of interconnected nanoparticles for asymmetric supercapacitors. Phys Chem Chem Phys 18(35):24471–24476Google Scholar

Copyright information

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

Authors and Affiliations

  • Nandhini Sonai Muthu
    • 1
  • Shobana Devi Samikannu
    • 1
  • Muralidharan Gopalan
    • 1
    Email author
  1. 1.Department of PhysicsThe Gandhigram Rural Institute (Deemed to be University)DindigulIndia

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