SCIENCE CHINA Materials, Volume 62, Issue 5: 633-644(2019) https://doi.org/10.1007/s40843-018-9367-3

Ball-flower-like carbon microspheres via a three-dimensional replication strategy as a high-capacity cathode in lithium–oxygen batteries

More info
  • ReceivedAug 14, 2018
  • AcceptedOct 16, 2018
  • PublishedNov 9, 2018


The robust porous architectures of active materials are highly desired for oxygen electrodes in lithium–oxygen batteries to enable high capacities and excellent reversibility. Herein, we report a novel three-dimensional replication strategy to fabricate three-dimensional architecture of porous carbon for oxygen electrodes in lithium–oxygen batteries. As a demonstration, ball-flower-like carbon microspheres assembled with tortuous hollow carbon nanosheets are successfully prepared by completely replicating the morphology of the nanostructured zinc oxide template and utilizing the polydopamine coating layer as the carbon source. When used as the active material for oxygen electrodes, the three-dimensional porous architecture of the prepared ball-flower-like carbon microspheres can accommodate the discharge product lithium peroxide and simultaneously maintain the ions and gas diffusion paths. Moreover, their high degrees of defectiveness by nitrogen doping provide sufficient active sites for oxygen reduction/evolution reaction. Thus the prepared ball-flower-like carbon microspheres demonstrate a high capacity of 9,163.7 mA h g−1 and excellent reversibility. This work presents an effective way to prepare three-dimensional architectures of porous carbon by replicating the controllable nanostructures of transition metal oxide templates for energy storage and conversion applications.

Funded by

grants from the National Natural Science Foundation of China(21673169,51672205)

the National Key R&D Program of China(2016YFA0202602)

the Research Start-Up Fund from Wuhan University of Technology

and the Fundamental Research Funds for the Central Universities(WUT:,2017IB005,2016IVA083)


This work was supported by grants from the National Natural Science Foundation of China (21673169 and 51672205), the National Key R&D Program of China (2016YFA0202602), the Research Start-Up Fund from Wuhan University of Technology, and the Fundamental Research Funds for the Central Universities (WUT: 2017IB005, 2016IVA083).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Xiao L, Yi J, Meng W and Wang S performed the experiments; Xiao L and Liu J wrote the paper. All authors contributed to the general discussion.

Author information

Liang Xiao received his PhD degree in physical chemistry from Wuhan University. He worked at Pacific Northwest National Laboratory as a visiting scholar for one year from 2013 to 2014. He is currently a Professor at the School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology. His current research focuses on nanostructured materials for lithium ion batteries and metal air batteries.

Jinping Liu received his PhD degree from Central China Normal University in June 2009. During 2008–2011, he did visiting and post-doctoral research at Nanyang Technological University in Singapore. He is currently Chair Professor at Wuhan University of Technology. His research interest includes the synthesis and electrochemical applications (batteries, supercapacitors & electrocatalysis) of nanostructures.


Supplementary information

Supplementary data are available in the online version of the paper.


[1] Lu J, Li L, Park JB, et al. Aprotic and aqueous Li–O2 batteries. Chem Rev, 2014, 114: 5611-5640 CrossRef PubMed Google Scholar

[2] Wang L, Zhang Y, Liu Z, et al. Understanding oxygen electrochemistry in aprotic Li–O2 batteries. Green Energy Environ, 2017, 2: 186-203 CrossRef Google Scholar

[3] Feng N, He P, Zhou H. Critical challenges in rechargeable aprotic Li-O2 batteries. Adv Energy Mater, 2016, 6: 1502303 CrossRef Google Scholar

[4] Aurbach D, McCloskey BD, Nazar LF, et al. Advances in understanding mechanisms underpinning lithium–air batteries. Nat Energy, 2016, 1: 16128 CrossRef ADS Google Scholar

[5] Adams BD, Radtke C, Black R, et al. Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge. Energy Environ Sci, 2013, 6: 1772-1778 CrossRef Google Scholar

[6] Peng Z, Freunberger SA, Chen Y, et al. A reversible and higher-rate Li-O2 battery. Science, 2012, 337: 563-566 CrossRef PubMed ADS Google Scholar

[7] Viswanathan V, Thygesen KS, Hummelshøj JS, et al. Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li-O2 batteries. J Chem Phys, 2011, 135: 214704 CrossRef PubMed ADS Google Scholar

[8] Liu Y, He P, Zhou H. Rechargeable solid-state Li-air and Li-S batteries: Materials, construction, and challenges. Adv Energy Mater, 2018, 8: 1701602 CrossRef Google Scholar

[9] Song K, Agyeman DA, Jung J, et al. A review of the design strategies for tailored cathode catalyst materials in rechargeable Li-O2 batteries. Isr J Chem, 2015, 55: 458-471 CrossRef Google Scholar

[10] Ma Z, Yuan X, Li L, et al. A review of cathode materials and structures for rechargeable lithium–air batteries. Energy Environ Sci, 2015, 8: 2144-2198 CrossRef Google Scholar

[11] Yin YB, Xu JJ, Liu QC, et al. Macroporous interconnected hollow carbon nanofibers inspired by golden-toad eggs toward a binder-free, high-rate, and flexible electrode. Adv Mater, 2016, 28: 7494-7500 CrossRef PubMed Google Scholar

[12] Guo Z, Zhou D, Dong XL, et al. Ordered hierarchical mesoporous/macroporous carbon: a high-performance catalyst for rechargeable Li-O2 batteries. Adv Mater, 2013, 25: 5668-5672 CrossRef PubMed Google Scholar

[13] Shu C, Li B, Zhang B, et al. Hierarchical nitrogen-doped graphene/carbon nanotube composite cathode for lithium-oxygen batteries. ChemSusChem, 2015, 8: 3973-3976 CrossRef PubMed Google Scholar

[14] Sun B, Huang X, Chen S, et al. Porous graphene nanoarchitectures: an efficient catalyst for low charge-overpotential, long life, and high capacity lithium–oxygen batteries. Nano Lett, 2014, 14: 3145-3152 CrossRef PubMed ADS Google Scholar

[15] Lu J, Lei Y, Lau KC, et al. A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries. Nat Commun, 2013, 4: 2383 CrossRef PubMed ADS Google Scholar

[16] Franco AA, Xue KH. Carbon-based electrodes for lithium air batteries: Scientific and technological challenges from a modeling perspective. ECS J Solid State Sci Technol, 2013, 2: M3084-M3100 CrossRef Google Scholar

[17] Tran C, Yang XQ, Qu D. Investigation of the gas-diffusion-electrode used as lithium/air cathode in non-aqueous electrolyte and the importance of carbon material porosity. J Power Sources, 2010, 195: 2057-2063 CrossRef ADS Google Scholar

[18] Yang X, He P, Xia Y. Preparation of mesocellular carbon foam and its application for lithium/oxygen battery. Electrochem Commun, 2009, 11: 1127-1130 CrossRef Google Scholar

[19] Nie H, Zhang H, Zhang Y, et al. Nitrogen enriched mesoporous carbon as a high capacity cathode in lithium–oxygen batteries. Nanoscale, 2013, 5: 8484-8487 CrossRef PubMed ADS Google Scholar

[20] Kang J, Li OL, Saito N. Hierarchical meso–macro structure porous carbon black as electrode materials in Li–air battery. J Power Sources, 2014, 261: 156-161 CrossRef ADS Google Scholar

[21] Xiao J, Mei D, Li X, et al. Hierarchically porous graphene as a lithium–air battery electrode. Nano Lett, 2011, 11: 5071-5078 CrossRef PubMed ADS Google Scholar

[22] Wang ZL, Xu D, Xu JJ, et al. Graphene oxide gel-derived, free-standing, hierarchically porous carbon for high-capacity and high-rate rechargeable Li-O2 batteries. Adv Funct Mater, 2012, 22: 3699-3705 CrossRef Google Scholar

[23] Lin Y, Moitoso B, Martinez-Martinez C, et al. Ultrahigh-capacity lithium–oxygen batteries enabled by dry-pressed holey graphene air cathodes. Nano Lett, 2017, 17: 3252-3260 CrossRef PubMed ADS Google Scholar

[24] McCloskey BD, Speidel A, Scheffler R, et al. Twin problems of interfacial carbonate formation in nonaqueous Li–O2 batteries. J Phys Chem Lett, 2012, 3: 997-1001 CrossRef PubMed Google Scholar

[25] Ottakam Thotiyl MM, Freunberger SA, Peng Z, et al. The carbon electrode in nonaqueous Li–O2 cells. J Am Chem Soc, 2013, 135: 494-500 CrossRef PubMed Google Scholar

[26] Yao X, Dong Q, Cheng Q, et al. Why do lithium-oxygen batteries fail: Parasitic chemical reactions and their synergistic effect. Angew Chem Int Ed, 2016, 55: 11344-11353 CrossRef PubMed Google Scholar

[27] Sun B, Chen S, Liu H, et al. Mesoporous carbon nanocube architecture for high-performance lithium-oxygen batteries. Adv Funct Mater, 2015, 25: 4436-4444 CrossRef Google Scholar

[28] Liu Y, Ai K, Lu L. Polydopamine and its derivative materials: Synthesis and promising applications in energy, environmental, and biomedical fields. Chem Rev, 2014, 114: 5057-5115 CrossRef PubMed Google Scholar

[29] Xiao L, Mei D, Cao M, et al. Effects of structural patterns and degree of crystallinity on the performance of nanostructured ZnO as anode material for lithium-ion batteries. J Alloys Compd, 2015, 627: 455-462 CrossRef Google Scholar

[30] Kuo CL, Kuo TJ, Huang MH. Hydrothermal synthesis of ZnO microspheres and hexagonal microrods with sheetlike and platelike nanostructures. J Phys Chem B, 2005, 109: 20115-20121 CrossRef PubMed Google Scholar

[31] Kaneko K. Determination of pore size and pore size distribution. J Membrane Sci, 1994, 96: 59-89 CrossRef Google Scholar

[32] Zhang Y, Zhang H, Li J, et al. The use of mixed carbon materials with improved oxygen transport in a lithium-air battery. J Power Sources, 2013, 240: 390-396 CrossRef Google Scholar

[33] Horstmann B, Gallant B, Mitchell R, et al. Rate-dependent morphology of Li2O2 growth in Li–O2 batteries. J Phys Chem Lett, 2013, 4: 4217-4222 CrossRef PubMed Google Scholar

[34] Kichambare P, Kumar J, Rodrigues S, et al. Electrochemical performance of highly mesoporous nitrogen doped carbon cathode in lithium–oxygen batteries. J Power Sources, 2011, 196: 3310-3316 CrossRef ADS Google Scholar

[35] Xie J, Yao X, Cheng Q, et al. Three dimensionally ordered mesoporous carbon as a stable, high-performance Li-O2 battery cathode. Angew Chem Int Ed, 2015, 54: 4299-4303 CrossRef PubMed Google Scholar

  • Scheme 1

    Illustration of the three-dimensional replication strategy.

  • Figure 1

    SEM images of (a) ZnO microspheres template and ball-flower-like carbon microspheres: (b) CF−50, (c) CF−80, and (d) CF−100.

  • Figure 2

    TEM images of (a) CF−50, (b) CF−80, and (c) CF−100, HR-TEM images of (d, e) CF−100.

  • Figure 3

    N2 sorption isotherms and inserted BJH pore size distributions of (a) SP and the prepared ball-flower-like carbon materials: (b) CF−100, (c) CF−80, (d) CF−50.

  • Figure 4

    (a) The thermogravimetric and differential thermal curves and (b) the Raman spectrum of CF−100; the XPS spectra of CF−100: (c) survey spectrum, (d) N 1s, (e) C 1s, and (f) O 1s.

  • Figure 5

    Voltage profiles of (a) SP, (b) CF−100, (c) CF−80, and (d) CF−50 at 100, 200, and 300 mA g−1 in the first cycle from 2.2 to 4.5 V.

  • Figure 6

    (a) Raman spectrum and (b, c) SEM images of discharged CF−50 electrode with a curtailed capacity of 1,000 mA h g−1; (d, e) SEM images of charged CF−50 electrode; (f, g) SEM images of CF−50 electrode discharged to 2.2 V.

  • Figure 7

    Voltage profiles of SP and CF−Xs with a curtailed specific capacity of 1,000 mA h g−1 at the current density of 100 mA g−1. The thermodynamic equilibrium potential (2.96 V) of oxygen electrode in the aprotic electrolyte is denoted with the dashed line, when the discharge product is Li2O2.

  • Figure 8

    Voltage profiles of CF−Xs during cycling at 100 mA g−1 with a curtailed specific capacity of 500 mA h g−1: (a) CF−100, (b) CF−80 and (c) CF−50; (d) the cycle number comparison of SP and CF−Xs.

  • Table 1   The structural properties of SP and CF−Xs






    SBET(m2 g−1)





    Vtotal(cm3 g−1)





  • Table 2   Full-discharge properties of previously reported Li−O batteries with nanostructured carbon-based oxygen cathodes compared to this work


    Electrode preparation

    Mass loading (mg cm−2)


    Current density

    Discharge capacity

    Publication year [Ref]

    Gravimetric (mA g−1)

    Areal (mA cm−2)

    Gravimetric (mA h g−1)

    Areal (mA h cm−2)

    Ball-flower-like carbon microspheres (CF−50)



    1 mol L−1 LiTFSI in TEGDME





    This work

    Mesocellular carbon foam

    Dry Compression


    1 mol L−1 LiClO4 in PC





    2009 [18]


    Dry rolling


    1 mol L−1 LiTFSI in Triglyme





    2011 [21]

    3D porous graphene framework

    Free standing


    1 mol L−1 LiTFSI in DME





    2012 [22]

    Ketjen black EC600JD and super P (weight ratio of 5:1)



    1 mol L−1 LiClO4 in PC





    2013 [32]

    Nitrogen enriched mesoporous carbon




    1 mol L−1 LiTFSI in TEGDME





    2013 [19]

    Hierarchical meso/macro structure porous carbon black



    1 mol L−1 LiClO4 in EC/PC (1:1)





    2014 [20]

    Mesoporous carbon nanocube



    0.1 mol L−1 LiClO4 in DMSO





    2015 [27]

    Three dimensionally ordered mesoporous carbon



    1.0 mol L−1 LiClO4 in TEGDME





    2015 [35]

    Hierarchical macroporous active carbon fiber



    0.05 mol L−1 LiI and 1 mol L−1 LiCF3SO3 in TEGDME





    2016 [11]

    Holey graphene

    Dry Compression


    1 mol L−1 LiTFSI in TEGDME





    2017 [23]

Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有