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Cobalt oxide thin films for high capacity and stable Li-ion battery anode

  • Anto P. Varghese
  • Shantikumar Nair
  • Dhamodaran SanthanagopalanEmail author
Original Paper
  • 36 Downloads

Abstract

Here, we report reactive DC-sputter deposited Co3O4 thin films as a promising and stable Li-ion battery anode. Thin films were deposited on stainless steel by reactive sputtering of cobalt target in O2 atmosphere. X-ray diffraction and X-ray photo electron spectroscopy confirm the formation of Co3O4 crystal structure and absence of other impurities. The electron microscopy analysis shows a columnar growth morphology of the thin films while high resolution images reveal that the film is composed of ultra-small nanoparticles of average size of 5 nm. Fabricated half cells upon cycling between 3.0 and 0.01 V exhibit a stable capacity of 1125 mAh/g at a current density of 1 A/g for 100 cycles. Moreover, the electrode exhibited excellent rate capability and stability at higher rates; at current density of 10 A/g, a capacity close to 1000 mAh/g was observed. The excellent cycling stability of the cell was further confirmed by cycling at a high rate of 25 A/g (28 C) wherein the same was able to retain a capacity of 330 mAh/g even at the end of 1800 cycles. This enhanced performance could be related to the formation of 5-nm primary particles and columnar growth morphology, capable of reducing the lithium ion diffusion lengths and thus offered better kinetics even at high rates.

Keywords

Anode Co3O4 DC sputtering Li-ion battery Thin film 

Notes

Acknowledgements

DS acknowledges Science and Engineering Research Board, India for awarding of Ramanujan Fellowship (Ref: SB/S2/RJN-100/2014). The PVD cluster deposition system funded by Amrita is greatfully acknowledged. APV acknowledges financial support from Department of Science and Technology, India (SR/NM/PG-01/2015).

Supplementary material

10008_2018_4158_MOESM1_ESM.docx (2.2 mb)
ESM 1 (DOCX 2219 kb)

References

  1. 1.
    Wang X, Li X, Sun X, Li F, Liu Q, Wang Q, He D (2011) Nanostructured NiO electrode for high rate Li-ion batteries. J Mater Chem 21(11):3571–3573CrossRefGoogle Scholar
  2. 2.
    Wang L, Xu HW, Chen PC, Zhang DW, Ding CX, Chen CH (2009) Electrostatic spray deposition of porous Fe2O3 thin films as anode material with improved electrochemical performance for lithium-ion batteries. J Power Sources 193(2):846–850CrossRefGoogle Scholar
  3. 3.
    Lan Z, Que L, Wu W, Wu J (2015) Preparation of Pt-NiO/Co3O4 nanocompounds based counter electrodes from Pt-Ni/Co alloys for high efficient dye-sensitized solar cells. J Alloys Compd 646:80–85CrossRefGoogle Scholar
  4. 4.
    Zhang J, Lin J, Wu J, Xu R, Lai M, Gong C, Chen X, Zhou P (2016) Excellent electrochemical performance hierarchical Co3O4@Ni3S2 core/shell nanowire arrays for asymmetric supercapacitors. Electrochim Acta 207:87–96CrossRefGoogle Scholar
  5. 5.
    Jena A, Munichandraiah N, Shivashankara SA (2015) Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery. J Power Sources 277:198–204CrossRefGoogle Scholar
  6. 6.
    Donders ME, Knoops HCM, Kessels WMM, Notten PHL (2012) Co3O4 as anode material for thin film micro-batteries prepared by remote plasma atomic layer deposition. J Power Sources 203:72–77CrossRefGoogle Scholar
  7. 7.
    Zhou G, Wang DW, Li F, Zhang L, Li N, Wu ZS, Wen L, Lu GQ(M), Cheng HM (2010) Graphene-wrapped Fe3O4anode material with improved reversible capacity and cyclic stability for lithium ion batteries. Chem Mater 22(18):5306–5313CrossRefGoogle Scholar
  8. 8.
    Kim S-J, Kim E-J, Liu M, Shin H-C (2016) Cobalt oxide nanorods prepared by a template-free method for lithium battery application. J Electrochem Sci Technol 7(3):206–213CrossRefGoogle Scholar
  9. 9.
    Zhan L, Wang Y, Qiao W et al (2012) Co3O4 nanocages for high-performance anode material in lithium-ion batteries. J Phys Chem C 116:7227–7235CrossRefGoogle Scholar
  10. 10.
    Sun Y, Feng XY, Chen CH (2011) Hollow Co3O4 thin films as high performance anodes for lithium-ion batteries. J Power Sources 196(2):784–787CrossRefGoogle Scholar
  11. 11.
    Huang H, Zhu W, Tao X, Xia Y, Yu Z, Fang J, Gan Y, Zhang W (2012) Nanocrystal-constructed mesoporous single-crystalline Co3O4 nanobelts with superior rate capability for advanced lithium-ion batteries. ACS Appl Mater Interfaces 4(11):5974–5980CrossRefGoogle Scholar
  12. 12.
    Yan C, Chen G, Zhou X, Sun J, Lv C (2016) Template-based engineering of carbon-doped Co3O4 hollow nanofibers as anode materials for lithium-ion batteries. Adv Funct Mater 26(9):1428–1436CrossRefGoogle Scholar
  13. 13.
    Pan A, Wang Y, Xu W, Nie Z, Liang S, Nie Z, Wang C, Cao G, Zhang JG (2014) High-performance anode based on porous Co3O4 nanodiscs. J Power Sources 255:125–129CrossRefGoogle Scholar
  14. 14.
    Lu Y, Wang Y, Zou Y, Jiao Z, Zhao B, He Y, Wu M (2010) Macroporous Co3O4 platelets with excellent rate capability as anodes for lithium ion batteries. Electrochem Commun 12(1):101–105CrossRefGoogle Scholar
  15. 15.
    Kim H, Seo DH, Kim SW, Kim J, Kang K (2011) Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries. Carbon N Y 49(1):326–332CrossRefGoogle Scholar
  16. 16.
    Li B, Cao H, Shao J, Li G, Qu M, Yin G (2011) Co3O4@graphene composites as anode materials for high-performance lithium ion batteries. Inorg Chem 50(5):1628–1632CrossRefGoogle Scholar
  17. 17.
    Leng X, Wei S, Jiang Z, Lian J, Wang G, Jiang Q (2015) Carbon-encapsulated Co3O4 nanoparticles as anode materials with super lithium storage performance. Sci Rep 5(1):16629CrossRefGoogle Scholar
  18. 18.
    Wang H, Mao N, Shi J, Wang Q, Yu W, Wang X (2015) Cobalt oxide-carbon nanosheet nanoarchitecture as an anode for high-performance lithium-ion battery. ACS Appl Mater Interfaces 7(4):2882–2890CrossRefGoogle Scholar
  19. 19.
    Liao CL, Lee HY, Chang ST, Fung KZ (2006) Structural characterization and electrochemical properties of RF-sputtered nanocrystalline Co3O4 thin-film anode. J Power Sources 158(2):1379–1385CrossRefGoogle Scholar
  20. 20.
    Wang L, Liu B, Ran S, Huang H, Wang X, Liang B, Chen D, Shen G (2012) Nanorod-assembled Co3O4 hexapods with enhanced electrochemical performance for lithium-ion batteries. J Mater Chem 22(44):23541CrossRefGoogle Scholar
  21. 21.
    Huang G, Xu S, Lu S, Li L, Sun H (2014) Micro-/nanostructured Co3O4 anode with enhanced rate capability for lithium-ion batteries. ACS Appl Mater Interfaces 6(10):7236–7243CrossRefGoogle Scholar
  22. 22.
    Zhou X, Shi J, Liu Y, Su Q, Zhang J, du G (2014) Microwave irradiation synthesis of Co3O4 quantum dots/graphene composite as anode materials for Li-ion battery. Electrochim Acta 143:175–179CrossRefGoogle Scholar
  23. 23.
    Tan Y, Gao Q, Yang C, Yang K, Tian W, Zhu L (2015) One-dimensional porous nanofibers of Co3O4 on the carbon matrix from human hair with superior lithium ion storage performance. Sci Rep 5(1):12382CrossRefGoogle Scholar
  24. 24.
    Liu HC, Yen SK (2007) Characterization of electrolytic Co3O4 thin films as anodes for lithium-ion batteries. J Power Sources 166(2):478–484CrossRefGoogle Scholar
  25. 25.
    Binitha G, Ashish AG, Ramasubramonian D, Manikandan P, Shaijumon MM (2016) Lithium-ion batteries: 3D interconnected networks of graphene and flower-like cobalt oxide microstructures with improved Lithium storage. Adv Mater Interfaces 3(1):1500419CrossRefGoogle Scholar
  26. 26.
    Keppeler M, Srinivasan M (2017) Interfacial phenomena/capacities beyond conversion reaction occurring in nano-sized transition-metal-oxide-based negative electrodes in lithium-ion batteries: a review. ChemElectroChem 4(11):2727–2754CrossRefGoogle Scholar
  27. 27.
    Wang R, Xu C, Sun J, Liu Y, Gao L, Lin C (2013) Free-standing and binder-free lithium-ion electrodes based on robust layered assembly of graphene and Co3O4 nanosheets. Nanoscale 5(15):6960–6967CrossRefGoogle Scholar
  28. 28.
    Wang Y, Zhang HJ, Lu L, Stubbs LP, Wong CC, Lin J (2010) Designed functional systems from peapod-like Co@carbon to Co3O4@carbon nanocomposites. ACS Nano 4(8):4753–4761CrossRefGoogle Scholar
  29. 29.
    Xing L, Chen Z, Xue X (2014) Controllable synthesis Co3O4 nanorods and nanobelts and their excellent lithium storage performance. Solid State Sci 32:88–93CrossRefGoogle Scholar
  30. 30.
    Zheng J, Zhang B (2014) Facile chemical bath deposition of Co3O4 nanowires on nickel foam directly as conductive agent- and binder-free anode for lithium ion batteries. Ceram Int 40(7):11377–11380CrossRefGoogle Scholar
  31. 31.
    Mo Y, Ru Q, Song X, Hu S, An B (2014) A novel dendritic crystal Co3O4 as high-performance anode materials for lithium-ion batteries. J Appl Electrochem 44(7):781–788CrossRefGoogle Scholar
  32. 32.
    Li Z, Yu X-Y, Paik U (2016) Facile preparation of porous Co3O4 nanosheets for high-performance lithium ion batteries and oxygen evolution reaction. J Power Sources 310:41–46CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Anto P. Varghese
    • 1
  • Shantikumar Nair
    • 1
  • Dhamodaran Santhanagopalan
    • 1
    Email author
  1. 1.Centre for Nanosciences and Molecular MedicineAmrita Vishwa Vidyapeetham, AIMS (P.O)KochiIndia

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