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Preparation of Co3O4 hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries

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Abstract

A flexible Co3O4 hollow microsphere/graphene/carbon nanotube hybrid film is successfully prepared through a facile filtration strategy and a subsequent thermally treated process. The composition, morphology, and structure of the as-prepared film are characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscopy, and transmission electron microscopy. Based on the morphology characterizations on the hybrid film, the Co3O4 hollow microspheres are uniformly and closely attached on three-dimensional (3D) graphene/carbon nanotubes (GR/CNTs) network, which decreases the agglomeration of Co3O4 microspheres effectively. In this hybrid film, the 3D GR/CNT network which enhances conductance as well as prevents aggregation is a benefit to help Co3O4 to exert its lithium storage capabilities sufficiently. When used as a binder-free anode material for lithium-ion batteries, the hybrid film delivers excellent electrochemical properties involving reversible capacity (863 mAh g−1 at a current density of 100 mA g−1) and rate performance (185 mAh g−1 at a current density of 1600 mA g−1).

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References

  1. Abe H, Kubota M, Nemoto M, Masuda Y, Tanaka Y, Munakata H, Kanamura K (2016) High-capacity thick cathode with a porous aluminum current collector for lithium secondary batteries. J Power Sources 334:78–85

    Article  CAS  Google Scholar 

  2. Huang GY, Xu SM, Xu ZH, Sun HY, Li LY (2014) Core–shell ellipsoidal MnCo2O4 anode with micro-/nano-structure and concentration gradient for lithium-ion batteries. ACS Appl Mater Interfaces 6:21325–21334

    Article  CAS  Google Scholar 

  3. Zhang YZ, Chen L, Meng Y, Xie J, Guo Y, Xiao D (2016) Lithium and sodium storage in highly ordered mesoporous nitrogen-doped carbons derived from honey. J Power Sources 335:20–30

    Article  CAS  Google Scholar 

  4. Bai L, Fang F, Zhao YY, Liu YG, Li JP, Huang GY, Sun HY (2014) A sandwich structure of mesoporous anatase TiO2 sheets and reduced graphene oxide and its application as lithium-ion battery electrodes. RSC Adv 4:43039–43046

    Article  CAS  Google Scholar 

  5. Xiao CL, Zhang SC, Wang SB, Xing YL, Lin RX, Wei X, Wang WX (2016) ZnO nanoparticles encapsulated in a 3D hierarchical carbon framework as anode for lithium ion battery. Electrochim Acta 189:245–251

    Article  CAS  Google Scholar 

  6. Xiao SN, Pan DL, Wang LJ, Zhang ZZ, Lyu ZY, Dong WH, Chen XL, Zhang DQ, Chen W, Li HX (2016) Porous CuO nanotubes/graphene with sandwich architecture as high-performance anodes for lithium-ion batteries. Nano 8:19343–19351

    CAS  Google Scholar 

  7. Wang BB, Wang G, Zheng ZZ, Wang H, Bai JT, Bai JB (2013) Carbon coated Fe3O4 hybrid material prepared by chemical vapor deposition for high performance lithium-ion batteries. Electrochim Acta 106:235–243

    Article  CAS  Google Scholar 

  8. Huang GY, Xu SM, Cheng YB, Zhang WJ, Li J, Kang XH (2015) NiO nanosheets with large specific surface area for lithium-ion batteries and supercapacitors. Int J Electrochem Sci 10:2594–2601

    CAS  Google Scholar 

  9. Liu CF, Zhang CK, Song HQ, Zhang CP, Liu YG, Nan XH, Cao GZ (2016) Mesocrystal MnO cubes as anode for Li-ion capacitors. Nano Energy 22:290–300

    Article  CAS  Google Scholar 

  10. Huang GY, Xu SM, Yang Y, Sun HY, Li ZB, Chen Q, Lu SS (2014) Micro-spherical CoCO3 anode for lithium-ion batteries. Mater Lett 131:236–239

    Article  CAS  Google Scholar 

  11. Huang GY, Xu SM, Yang Y, Chen YB, Li ZB (2015) Rapid-rate capability of micro-/nano-structured CoO anodes with different morphologies for lithium-ion batteries. Int J Electrochem Sci 10:10587–10596

  12. Yan CS, Chen G, Zhou X, Sun JX, Lv C (2016) Template-based engineering of carbon-doped Co3O4 hollow nanofibers as anode materials for lithium-ion batteries. Adv Funct Mater 26:1428–1436

    Article  CAS  Google Scholar 

  13. Wang YQ, Geng FS, Yue XB, Yuan AB, Xu JQ (2016) Enhanced lithium storage performance of a self-assembled hierarchical porous Co3O4/VGCF hybrid high-capacity anode material for lithium-ion batteries. Ionics:1–8

  14. Xiao XL, Liu XF, Zhao H, Chen DF, Liu FZ, Xiang JH, Hu ZB, Li YD (2012) Facile shape control of Co3O4 and the effect of the crystal plane on electrochemical performance. Adv Mater 24:5762–5766

    Article  CAS  Google Scholar 

  15. Huang GY, Xu SM, Li LY, Wang XJ, Lu SS (2014) Synthesis and modification of a lamellar Co3O4 anode for lithium-ion batteries. Acta Phys -Chim sin 30:1121–1126

    CAS  Google Scholar 

  16. Huang GY, Xu SM, Lu SS, Li LY, Sun HY (2014) Porous polyhedral and fusiform Co3O4 anode materials for high-performance lithium-ion batteries. Electrochim Acta 135:420–427

    Article  CAS  Google Scholar 

  17. Zhang DW, Qian A, Chen JJ, Wen JW, Wang L, Chen CH (2012) Electrochemical performances of nano-Co3O4 with different morphologies as anode materials for Li-ion batteries. Ionics 18:591–597

    Article  CAS  Google Scholar 

  18. Ma JM, Manthiram A (2012) Precursor-directed formation of hollow Co3O4 nanospheres exhibiting superior lithium storage properties. RSC Adv 2:3187

    Article  CAS  Google Scholar 

  19. Huang GY, Xu SM, Lu SS, Li LY, Sun HY (2014) Micro-/nanostructured Co3O4 anode with enhanced rate capability for lithium-ion batteries. ACS applied materials & interfaces 6:7236–7243

  20. Fan S, Liu XJ, Li YF, Yan E, Wang CH, Liu JH, Zhang Y (2013) Non-aqueous synthesis of crystalline Co3O4 nanoparticles for lithium-ion batteries. Mater Lett 91:291–293

    Article  CAS  Google Scholar 

  21. Wang DL, Yu YC, He H, Wang J, Zhou WD, Abruña HD (2015) Template-free synthesis of hollow-structured Co3O4 nanoparticles as high-performance anodes for lithium-ion batteries. ACS Nano 9:1775–1781

    Article  CAS  Google Scholar 

  22. Hung GY, Xu SM, Yang Y, Sun HY, Xu ZH (2016) Synthesis of porous MnCo2O4 microspheres with yolk–shell structure induced by concentration gradient and the effect on their performance in electrochemical energy storage. RSC Adv 6:10763–10774

    Article  Google Scholar 

  23. Tung VC, Chen LM, Allen MJ, Wassei JK, Nelson K, Kaner RB, Yang Y (2009) Low-temperature solution processing of graphene-carbon nanotube hybrid materials for high-performance transparent conductors. Nano Lett 9:1949–1955

    Article  CAS  Google Scholar 

  24. Ye MH, Li CX, Zhao Y, Qu LT (2016) Graphene decorated with bimodal size of carbon polyhedrons for enhanced lithium storage. Carbon 106:9–19

    Article  CAS  Google Scholar 

  25. Shen LF, Zhang XG, Li HS, Yuan CZ, Cao GZ (2011) Design and tailoring of a three-dimensional TiO2–graphene–carbon nanotube nanocomposite for fast lithium storage. J Phys Chem Lett 2:3096–3101

    Article  CAS  Google Scholar 

  26. Su XQ, Wang G, Li WL, Bai JT, Wang H (2013) A simple method for preparing graphene nano-sheets at low temperature. Adv Powder Technol 24:317–323

    Article  CAS  Google Scholar 

  27. Zhao JJ, Liu YM, Quan X, Chen S, Zhao HM, Yu HT (2016) Nitrogen and sulfur co-doped graphene/carbon nanotube as metal-free electrocatalyst for oxygen evolution reaction: the enhanced performance by sulfur doping. Electrochim Acta 204:169–175

    Article  CAS  Google Scholar 

  28. Wang JG, Zhang CB, Kang FY (2015) Nitrogen-enriched porous carbon coating for manganese oxide nanostructures toward high-performance lithium-ion batteries. ACS Appl Mater Interfaces 7:9185–9194

    Article  CAS  Google Scholar 

  29. Sun HT, Sun X, Hu T, Yu MP, Lu FY, Lian J (2014) Graphene-wrapped mesoporous cobalt oxide hollow spheres anode for high-rate and long-life lithium ion batteries. J Phys Chem C 118:2263–2272

    Article  CAS  Google Scholar 

  30. Xiong SL, Chen JS, Lou XW, Zeng HC (2012) Mesoporous Co3O4and CoO@C topotactically transformed from chrysanthemum-like Co(CO3)0.5(OH)·0.11H2O and their lithium-storage properties. Adv Funct Mater 22:861–887

    Article  CAS  Google Scholar 

  31. Zhao J, Liu ZS, Qin YQ, Hu WB (2014) Fabrication of Co3O4/graphene oxide hybrids using supercritical fluid and their catalytic application for the decomposition of ammonium perchlorate. Cryst Eng Comm 16:2001

    Article  CAS  Google Scholar 

  32. Liao QY, Li N, Jin SX, Yang GW, Wang CX (2015) All-solid-state symmetric supercapacitor based on Co3O4 nanoparticles on vertically aligned graphene. ACS Nano 9:5310–5317

    Article  CAS  Google Scholar 

  33. Yan N, Hu L, Li Y, Wang Y, Zhong H, Hu XY, Kong XK, Chen Q (2012) Co3O4 nanocages for high-performance anode material in lithium-ion batteries. J Phys Chem C 116:7227–7235

    Article  CAS  Google Scholar 

  34. Zhang MG, Smith A, Gorski W (2004) Carbon nanotube-chitosan system for electrochemical sensing based on dehydrogenase enzymes. Anal Chem 76:5045–5050

    Article  CAS  Google Scholar 

  35. Sun Y, Feng XY, Chen CH (2011) Hollow Co3O4 thin films as high performance anodes for lithium-ion batteries. J Power Sources 196:784–787

    Article  CAS  Google Scholar 

  36. Larcher D, Sudant G, Patrice R, Tarascon JM (2003) Some insights on the use of polyols-based metal alkoxides powders as precursors for tailored metal-oxides particles. Chem Mater 15:3543–3551

    Article  CAS  Google Scholar 

  37. Huang GY, Guo XY, Cao X, Tian QH, Sun HY (2016) 3D network single-phase Ni0.9Zn0.1O as anode materials for lithium-ion batteries. Nano Energy 28:338–345

    Article  CAS  Google Scholar 

  38. Huang GY, Guo XY, Cao X, Tian QH, Sun HY (2017) Formation of graphene-like 2D spinel MnCo2O4 and its lithium storage properties. J Alloys Compd 695:2937–2944

    Article  CAS  Google Scholar 

  39. Huang GY, Zhang WJ, Xu SM, Li YJ, Yang Y (2016) Microspherical ZnO synthesized from a metal-organic precursor for supercapacitors. Ionics 22:2169–2174

    Article  CAS  Google Scholar 

  40. Du W, Liu RM, Jiang YW, Lu QY, Fan YZ, Gao F (2013) Facile synthesis of hollow Co3O4 boxes for high capacity supercapacitor. J Power Sources 227:101–105

    Article  CAS  Google Scholar 

  41. Wu ZS, Ren WC, Wen L, Gao LB, Zhao JP, Chen ZP, Zhou GM, Li F, Cheng HM (2010) Graphene anchored with Co3O4 nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance. ACS Nano 4:3187–3194

    Article  CAS  Google Scholar 

  42. Huang G, Zhang FF, Du XC, Qin YL, Yin DM, Wang LM (2015) Metal organic frameworks route to in situ insertion of multiwalled carbon nanotubes in Co3O4 polyhedra as anode materials for lithium-ion batteries. ACS Nano 9:1592–1599

    Article  CAS  Google Scholar 

  43. Huang GY, Xu SM, Wang JL, Li LY, Wang XJ (2013) Recent development of Co3O4 and its composites as anode materials of lithium-ion batteries. Acta Chim sin 71:1589–1597

    Article  CAS  Google Scholar 

  44. Tan YL, Gao QM, Li ZY, Tian WQ, Qian WW, Yang CX, Zhang H (2016) Unique 1D Co3O4 crystallized nanofibers with (220) oriented facets as high-performance lithium ion battery anode material. Scientific reports 6.

  45. Liao JY, Higgins D, Lui G, Chabot V, Xiao XC, Chen ZW (2013) Multifunctional TiO2–C/MnO2 core–double-shell nanowire arrays as high-performance 3D electrodes for lithium ion batteries. Nano Lett 13:5467–5473

    Article  CAS  Google Scholar 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (21301140), Natural Science Basic Research Plan in Shaanxi Province of China (2016JM2027), Shaanxi Science & Technology Coordination & Innovation Project (2016KTZDGY09-09), and Xi’an Industrial Technology Innovation Project-Technology Transfer Promoting Program (CXY1511-10).

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Authors and Affiliations

  1. State Key Lab Incubation Base of Photoelectric Technology and Functional Materials, International Collaborative Center on Photoelectric Technology and Nano Functional Materials, Institute of Photonics & Photo-Technology, Northwest University, Xi’an, 710069, People’s Republic of China

    Fei Li & Gang Wang

  2. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), College of Chemistry & Materials Science, Northwest University, Xi’an, 710069, People’s Republic of China

    Gaohong Zhai & Hui Wang

  3. Key Laboratory of Fine Chemicals Petroleum, Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an, 710054, People’s Republic of China

    Haijing Ren

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  1. Fei Li
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  2. Gaohong Zhai
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  3. Haijing Ren
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  4. Gang Wang
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  5. Hui Wang
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Correspondence to Gang Wang or Hui Wang.

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Li, F., Zhai, G., Ren, H. et al. Preparation of Co3O4 hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries. Ionics 24, 111–120 (2018). https://doi.org/10.1007/s11581-017-2173-z

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  • DOI: https://doi.org/10.1007/s11581-017-2173-z

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