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Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo2O4 microspheres and their lithium storage properties

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Abstract

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo2O4 microspheres have been fabricated by calcinating the Zn1/3Co2/3CO3 precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo2O4 microspheres exhibit an initial discharge capacity of 1,369 mAh g−1 (3,244.5 F cm−3) and retain stable capacity of 800 mAh g−1 (1,896 F cm−3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo2O4 3D hierarchical structures provide a large number of active surface position for Li+ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.

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References

  1. Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM (2000) Nano-sized transition-metal oxides as negative-electrode materials for lithium ion batteries. Nature 407:496–499

    Article  CAS  Google Scholar 

  2. Li H, Wang Z, Chen L, Huang X (2009) Research on advanced materials for Li-ion batteries. Adv Mater 21:4593–4607

    Article  Google Scholar 

  3. Aricò A, Bruce P, Scrosati B, Van Schalkwijk Tarascon W (2005) Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 4:366–377

    Article  Google Scholar 

  4. Li J, Xiong S, Liu Y, Ju Z, Qian Y (2013) High electrochemical performance of monodisperse NiCo2O4 mesoporous microspheres as an anode material for Li-ion batteries. ACS Appl Mater Interfaces 5:981–988

    Article  CAS  Google Scholar 

  5. Liu J, Liu C, Wang Y, Liu W, Ma Z, Ji S, Wang J, Zhou Y, Hodgson P, Li Y (2013) Facile synthesis of NiCo2O4 nanorod arrays on Cu conductive substrates as superior anode materials for high-rate Li-ion batteries. CryEngComm 15:1578–1585

    Article  CAS  Google Scholar 

  6. Li J, Xiong S, Li X, Qian Y (2013) A facile route to synthesize multiporous MnCo2O4 and CoMn2O4 spinel quasi-hollow spheres with improved lithium storage properties. Nanoscale 5:2045–2054

    Article  CAS  Google Scholar 

  7. Li J, Wang J, Liang X, Zhang Z, Liu H, Qian Y, Xiong S (2014) Hollow MnCo2O4 submicrospheres with multilevel interiors: from mesoporous spheres to yolk-in-double-shell structures. ACS Appl Mater Interfaces 6:24–30

    Article  Google Scholar 

  8. Sun S, Wen Z, Jin J, Cui Y, Lu Y (2013) Synthesis of ordered mesoporous CuCo2O4 with different textures as anode material for lithium ion battery. Micropor Mesopor Mater 169:242–247

    Article  CAS  Google Scholar 

  9. Liu B, Zhang J, Wang X, Chen G, Chen D, Zhou C, Shen G (2013) Hierarchical three-dimensional ZnCo2O4 nanowire arrays/carbon cloth anodes for a novel class of high-performance flexible lithium-ion batteries. Nano Lett 12:3005–3011

    Article  Google Scholar 

  10. Hu L, Zhong H, Zheng X, Huang Y, Zhang P, Chen Q (2014) CoMn2O4 spinel hierarchical microspheres assembled with porous nanosheets as stable anodes for lithium-ion batteries. Sci Rep 2:1–8

    Google Scholar 

  11. Zhou L, Zhao D, Lou XW (2012) Double-shelled CoMn2O4 hollow microcubes as high-capacity anodes for lithium-ion batteries. Adv Mater 24:745–748

    Article  CAS  Google Scholar 

  12. Yuan C, Li J, Hou L, Zhang L, Zhang X (2014) Template-free fabrication of mesoporous hollow ZnMn2O4 sub-microspheres with enhanced lithium storage capability towards high-performance Li-ion batteries. Part Part Syst Charact 31:657–663

    Article  CAS  Google Scholar 

  13. Wang N, Ma X, Xu H, Chen L, Yue J, Niu F, Yang J, Qian Y (2014) Porous ZnMn2O4 microspheres as a promising anode material for advanced lithium-ion batteries. Nano Energy 6: 193–199

  14. Zhou L, Wu H, Zhu T, Lou X (2012) Facile preparation of ZnMn2O4 hollow microspheres as high-capacity anodes for lithium-ion batteries. J Mater Chem 22:827–829

    Article  CAS  Google Scholar 

  15. Ding Y, Yang Y, Shao H (2011) High capacity ZnFe2O4 anode material for lithium ion batteries. Electrochim Acta 56:9433–9438

    Article  CAS  Google Scholar 

  16. Guo X, Lu X, Fang X, Mao Y, Wang Z, Chen L, Xu X, Yang H, Liu Y (2010) Lithium storage in hollow spherical ZnFe2O4 as anode materials for lithium ion batteries. Electrochem Commun 12:847–850

    Article  CAS  Google Scholar 

  17. Li Z, Zhao T, Zhan X, Gao D, Xiao Q, Lei G (2010) High capacity three-dimensional ordered macroporous CoFe2O4 as anode material for lithium ion batteries. Electrochim Acta 55:4594–4598

    Article  CAS  Google Scholar 

  18. Wang Y, Su D, Ung A, Ahn J, Wang G (2012) Hollow CoFe2O4 nanospheres as a high capacity anode material for lithium ion batteries. Naonotechnology 23:1–7

    Google Scholar 

  19. Jin L, Qiu Y, Deng H, Li W, Li H, Yang S (2011) Hollow CuFe2O4 spheres encapsulated in carbon shells as an anode material for rechargeable lithium-ion batteries. Electrochim Acta 56:9127–9132

    Article  CAS  Google Scholar 

  20. Ding Y, Yang Y, Shao H (2012) Synthesis and characterization of nanostructured CuFe2O4 anode material for lithium ion battery. Solid State Ionic 217:27–33

    Article  CAS  Google Scholar 

  21. Sharma Y, Sharma N, Rao GVS, Chowdari BVR (2007) Nanophase ZnCo2O4 as a high performance anode material for Li-ion batteries. Adv Funct Mater 17:2855–2861

    Article  CAS  Google Scholar 

  22. Qiu Y, Yang S, Deng H, Jin L, Li W (2010) A novel nanostructured spinel ZnCo2O4 electrode material: morphology conserved transformation from a hexagonal shaped nanodisk precursor and application in lithium ion batteries. J Mater Chem 20:4439–4444

    Article  CAS  Google Scholar 

  23. Luo W, Hu X, Sun Y, Huang Y (2012) Electrospun porous ZnCo2O4 nanotubes as a high-performance anode material for lithium-ion batteries. J Mater Chem 22:8916–8921

    Article  CAS  Google Scholar 

  24. Du N, Xu Y, Zhang H, Yu J, Zhai C, Yang D (2011) Porous ZnCo2O4 nanowires synthesis via sacrificial templates: high-performance anode materials of Li-ion batteries. Inorg Chem 50:3320–3324

    Article  CAS  Google Scholar 

  25. Xie Q, Li F, Guo H, Wang L, Chen Y, Yue G, Peng D (2013) Template-free synthesis of amorphous double-shelled zinc-cobalt citrate hollow microspheres and their transformation to crystalline ZnCo2O4 microspheres. ACS Appl Mater Interfaces 5:5508–5517

    Article  CAS  Google Scholar 

  26. Hu L, Qu B, Li C, Chen Y, Mei L, Lei D, Chen L, Li Q, Wang T (2013) Facile synthesis of uniform mesoporous ZnCo2O4 microspheres as a high-performance anode material for Li-ion batteries. J Mater Chem A 1:5596–5602

    Article  CAS  Google Scholar 

  27. Bai J, Li X, Liu G, Qian Y, Xiong S (2014) Unusual formation of ZnCo2O4 3D hierarchical twin microspheres as a high-rate and ultralong-life lithium-ion battery anode material. Adv Funct Mater 24:3012–3020

    Article  CAS  Google Scholar 

  28. Liu H, Wang J (2013) One-pot synthesis of ZnCo2O4 nanorod anodes for high power lithium ions batteries. Electrochim Acta 92:371–375

    Article  CAS  Google Scholar 

  29. Long H, Shi T, Jiang S, Xi S, Chen R, Liu S, Liao G, Tang Z (2014) Synthesis of a nanowire self-assembled hierarchical ZnCo2O4 shell/Ni current collector core as binder-free anodes for high-performance Li-ion batteries. J Mater Chem A 2:3741–3748

    Article  CAS  Google Scholar 

  30. Hung T, Mohamed S, Shen C, Tsai Y, Chang W, Liu R (2013) Mesoporous ZnCo2O4 nanoflakes with bifunctional electrocatalytic activities toward efficiencies of rechargeable lithium–oxygen batteries in aprotic media. Nanoscale 5:12115–12119

    Article  CAS  Google Scholar 

  31. Kruk M, Jaroniec M (2001) Gas adsorption characterization of ordered organic–inorganic nanocomposite materials. Chem Mater 13:3169–3183

    Article  CAS  Google Scholar 

  32. Li J, Xiong S, Li X, Qian Y (2012) Spinel Mn1.5Co1.5O4 core-shell microspheres as Li-ion battery anode materials with a long cycle life and high capacity. J Mater Chem 22:23254–23259

    Article  CAS  Google Scholar 

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

  34. Xu J, Zhu Y (2012) Monodisperse Fe3O4 and γ-Fe2O3 magnetic mesoporous microspheres as anode materials for lithium-ion batteries. ACS Appl Mater Interface 4:4752–4757

    Article  CAS  Google Scholar 

  35. Mohamed S, Huang T, Chen C, Chen C, Hu S, Liu R, Wang K, Xing X, Liu H, Liu A, Hsieh M, Lee B (2013) Flower-like ZnCo2O4 nanowires: toward a high performance anode material for Li-ion batteries. RSC Adv 3:20143–20149

    Article  CAS  Google Scholar 

  36. Li J, Wang J, Wexler D, Shi D, Liang J, Liu H, Xiong S, Qian Y (2013) Simple synthesis of yolk-shelled ZnCo2O4 microspheres towards enhancing the electrochemical performance of lithium-ion batteries in conjunction with a sodium carboxymethyl cellulose binder. J Mater Chem A 1:15292–15299

    Article  CAS  Google Scholar 

  37. Choi S, Kang Y (2013) Yolk–shell, hollow, and single-crystalline ZnCo2O4 powders: preparation using a simple one-pot process and application in lithium-ion batteries. ChemSusChem 6:2111–2116

    Article  CAS  Google Scholar 

  38. 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 6:7236–7243

    Article  CAS  Google Scholar 

  39. He C, Wu S, Zhao N, Shi C, Liu E, Li J (2013) Carbon-encapsulated Fe3O4 nanoparticles as a high-rate lithium ion battery anode material. ACS Nano 5:4459–4469

    Article  Google Scholar 

  40. Jia X, Chen Z, Cui X, Peng Y, Wang X, Wang G, Wei F, Lu Y (2012) Building robust architectures of carbon and metal oxide nanocrystals toward high-performance anodes for lithium-ion batteries. ACS Nano 6:9911–9919

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work is supported by the MOST (Grant Nos. 2011CB935902, 2013CB934000, 2013AA050903, and 2010DFA72760) and the Tsinghua University Initiative Scientific Research Program (Grant Nos. 2010THZ08116, 2011THZ08139, 2011THZ01004, and 2012THZ08129) and State Key Laboratory of Automotive Safety and Energy (Grant No. ZZ2012-011).

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Authors and Affiliations

  1. Institute of Nuclear and New Energy Technology, Beijing Key Lab of Fine Ceramics, Tsinghua University, Beijing, 100084, People’s Republic of China

    Yuhong Jin, Li Wang, Yuming Shang, Jian Gao, Jianjun Li & Xiangming He

  2. State Key Laboratory of Automotive Safety and Energy, Tsinghua University, Beijing, 100084, People’s Republic of China

    Xiangming He

  3. Huadong Institute of Lithium Ion Battery, Zhangjiagang, Jiangsu, 215600, People’s Republic of China

    Jianjun Li

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  1. Yuhong Jin
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  2. Li Wang
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  3. Yuming Shang
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  4. Jian Gao
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  5. Jianjun Li
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Correspondence to Li Wang or Xiangming He.

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Jin, Y., Wang, L., Shang, Y. et al. Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo2O4 microspheres and their lithium storage properties. Ionics 21, 2743–2754 (2015). https://doi.org/10.1007/s11581-015-1480-5

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  • DOI: https://doi.org/10.1007/s11581-015-1480-5

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