A lithium–oxygen battery based on lithium superoxide

  • Nature volume 529, pages 377382 (21 January 2016)
  • doi:10.1038/nature16484
  • Download Citation


Batteries based on sodium superoxide and on potassium superoxide have recently been reported1,2,3. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research4,5,6,7,8 into the lithium–oxygen (Li–O2) battery because of its potential high energy density. Several studies9,10,11,12,13,14,15,16 of Li–O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime17. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form18 because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li–O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li–O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

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This work was primarily supported by the US Department of Energy under contract DE-AC02-06CH11357 from the Vehicle Technologies Office, Department of Energy, Office of Energy Efficiency and Renewable Energy. We also acknowledge support from the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center (EFRC) funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (X-ray measurements and analysis). We also acknowledge support from the University of Illinois-Chicago Chancellor Proof of Concept Fund (DEMS measurements). We acknowledge the Conn Renewable Energy Research Center at the University of Louisville for providing the access to the DEMS equipment. We acknowledge grants of computer time through INCITE awards on the BlueGene/Q computer at Argonne National Laboratory and allocations on the CNM Carbon Cluster at Argonne National Laboratory and the LCRC Fusion Cluster at Argonne National Laboratory. Use of the Advanced Photon Source and the Electron Microscopy Center, Center for Nanoscale Materials was supported by the US Department of Energy, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. We acknowledge financial support from the Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) funded by the Korea government Ministry of Knowledge Economy (no. 20124010203310), and from the Basic Science Research Program (no. NRF-2014R1A2A1A11049801). We acknowledge C. Barile, R. Rooney, R. Assary and P. Redfern for discussions and help on the lithium superoxide reaction mechanism.

Author information

Author notes

    • Jun Lu
    • , Yun Jung Lee
    • , Xiangyi Luo
    • , Kah Chun Lau
    •  & Mohammad Asadi

    These authors contributed equally to this work.


  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Jun Lu
    • , Dengyun Zhai
    • , Zonghai Chen
    •  & Khalil Amine
  2. Department of Energy Engineering, Hanyang University, Seoul 133-791, South Korea

    • Yun Jung Lee
    • , Yo Sub Jeong
    • , Jin-Bum Park
    •  & Yang-Kook Sun
  3. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Xiangyi Luo
    • , Kah Chun Lau
    • , Hsien-Hau Wang
    • , Scott Brombosz
    •  & Larry A. Curtiss
  4. Department of Metallurgical Engineering, University of Utah, Salt Lake City, Utah 84112, USA

    • Xiangyi Luo
    •  & Zhigang Zak Fang
  5. Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, Illinois 60607, USA

    • Mohammad Asadi
    •  & Amin Salehi-Khojin
  6. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Jianguo Wen
    •  & Dean J. Miller
  7. Conn Center for Renewable Energy Research, University of Louisville, Louisville, Kentucky 40292, USA

    • Bijandra Kumar


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J.L. and K.A. designed the experiments; Y.J.L., J.-B.P. and Y.S.J. synthesized the cathode materials; J.L., D.J.M. and J.W. performed and analysed the TEM imaging experiments; J.L., X.L., L.A.C. and Z.C. performed and analysed the X-ray measurements; J.L., X.L., Z.Z.F., D.Z. and H.-H.W. tested the cathode materials; M.A., A.S.-K. and B.K. performed the DEMS measurements, H.-H.W., X.L. and S.B. performed the Raman, NMR, EPR and FTIR experiments, K.C.L. and L.A.C. were responsible for the theoretical computations. L.A.C., K.A. and Y.-K.S. supervised the project; L.A.C., J.L. and K.A. wrote the paper. All of the authors discussed the results and reviewed the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Yang-Kook Sun or Larry A. Curtiss or Khalil Amine.

Atomic coordinates for the LiO2 crystal structure from DFT can be obtained from the ICSD Database (http://www2.fiz-karlsruhe.de/icsd_home.html).

Supplementary information

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  1. 1.

    Supplementary Information

    This file contains Supplementary Figures 1-18, Supplementary Tables 1-3 and Supplementary References.


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