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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

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

Abstract

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)


Acknowledgment

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.


Supplement

Supplementary information

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


References

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  • 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

    Samples

    SP

    CF−100

    CF−80

    CF−50

    SBET(m2 g−1)

    60.0

    729.3

    772.1

    1007.8

    Vtotal(cm3 g−1)

    0.124

    0.907

    1.36

    2.66

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

    Materials

    Electrode preparation

    Mass loading (mg cm−2)

    Electrolyte

    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)

    Slurry

    1

    1 mol L−1 LiTFSI in TEGDME

    100

    0.1

    9163.7

    9.16

    This work

    Mesocellular carbon foam

    Dry Compression

    /

    1 mol L−1 LiClO4 in PC

    /

    0.1

    2500

    /

    2009 [18]

    Graphene

    Dry rolling

    2.1

    1 mol L−1 LiTFSI in Triglyme

    47.6

    0.1

    15000

    31.5

    2011 [21]

    3D porous graphene framework

    Free standing

    0.71

    1 mol L−1 LiTFSI in DME

    280

    0.2

    11060

    7.85

    2012 [22]

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

    Laminated

    6.7±0.4

    1 mol L−1 LiClO4 in PC

    30

    0.2

    1219

    8.2

    2013 [32]

    Nitrogen enriched mesoporous carbon

    Dry

    Compression

    3.39

    1 mol L−1 LiTFSI in TEGDME

    30

    0.1

    4500

    15.3

    2013 [19]

    Hierarchical meso/macro structure porous carbon black

    Slurry

    1.5

    1 mol L−1 LiClO4 in EC/PC (1:1)

    67

    0.1

    3600

    5.4

    2014 [20]

    Mesoporous carbon nanocube

    Slurry

    0.5

    0.1 mol L−1 LiClO4 in DMSO

    200

    0.1

    22390

    11.2

    2015 [27]

    Three dimensionally ordered mesoporous carbon

    Slurry

    0.5-1

    1.0 mol L−1 LiClO4 in TEGDME

    200

    0.1

    6300

    3.15

    2015 [35]

    Hierarchical macroporous active carbon fiber

    Free-standing

    /

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

    1000

    /

    13290

    /

    2016 [11]

    Holey graphene

    Dry Compression

    5

    1 mol L−1 LiTFSI in TEGDME

    20

    0.1

    7667

    37.3

    2017 [23]

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