Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

A lithium–oxygen battery based on lithium superoxide

Nature volume 529, pages 377–382 (2016)Cite this article

Subjects

Abstract

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.

Access through your institution
Buy or subscribe

This is a preview of subscription content, access via your institution

Access options

Access through your institution

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Morphology of Ir–rGO.
Figure 2: Electrochemical tests and discharge products.
Figure 3: Characterization of discharge products.
Figure 4: Density functional calculations.

Similar content being viewed by others

References

  1. Hartmann, P. et al. A rechargeable room-temperature sodium superoxide (NaO2) battery. Nature Mater. 12, 228–232 (2012)

    Article  ADS  Google Scholar 

  2. Hartmann, P. et al. A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery. Phys. Chem. Chem. Phys. 15, 11661–11672 (2013)

    Article  CAS  PubMed  Google Scholar 

  3. Ren, X. & Wu, Y. A low-overpotential potassium–oxygen battery based on potassium superoxide. J. Am. Chem. Soc. 135, 2923–2926 (2013)

    Article  CAS  PubMed  Google Scholar 

  4. Lu, J. et al. A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries. Nature Commun. 4, 2383 (2013)

    Article  ADS  Google Scholar 

  5. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li-O2 and Li-S batteries with high energy storage. Nature Mater. 11, 19–29 (2011)

    Article  ADS  Google Scholar 

  6. Lu, J. et al. Aprotic and aqueous Li–O2 batteries. Chem. Rev. 114, 5611–5640 (2014)

    Article  CAS  PubMed  Google Scholar 

  7. Lu, J. et al. Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries. Nature Commun. 5, 4895 (2014)

    Article  ADS  CAS  Google Scholar 

  8. Black, R., Lee, J.-H., Adams, B., Mims, C. A. & Nazar, L. F. The role of catalysts and peroxide oxidation in lithium–oxygen batteries. Angew. Chem. Int. Edn 52, 392–396 (2013)

    Article  CAS  Google Scholar 

  9. Zhai, D. et al. Raman evidence for late stage disproportionation in a Li–O2 battery. J. Phys. Chem. Lett. 5, 2705–2710 (2014)

    Article  CAS  PubMed  Google Scholar 

  10. Zhai, D. et al. Disproportionation in Li–O2 batteries based on a large surface area carbon cathode. J. Am. Chem. Soc. 135, 15364–15372 (2013)

    Article  CAS  PubMed  Google Scholar 

  11. Yang, J. et al. Evidence for lithium superoxide-like species in the discharge product of a Li-O2 battery. Phys. Chem. Chem. Phys. 15, 3764–3771 (2013)

    Article  ADS  CAS  PubMed  Google Scholar 

  12. Gittleson, F. S., Ryu, W.-H. & Taylor, A. D. Operando observation of the gold-electrolyte interface in Li-O2 batteries. ACS Appl. Mater. Interfaces 6, 19017–19025 (2014)

    Article  CAS  PubMed  Google Scholar 

  13. Gittleson, F. S. et al. Raman spectroscopy in lithium-oxygen battery systems. ChemElectroChem 2, 1446–1457 (2015)

    Article  CAS  Google Scholar 

  14. Olivares-Marín, M. et al. Spatial distributions of discharged products of lithium-oxygen batteries revealed by synchrotron X-ray transmission microscopy. Nano Lett. 15, 6932–6938 (2015)

    Article  ADS  PubMed  Google Scholar 

  15. Ryu, W.-H., Gittleson, F. S., Schwab, M., Goh, T. & Taylor, A. D. A mesoporous catalytic membrane architecture for lithium-oxygen battery systems. Nano Lett. 15, 434–441 (2015)

    Article  ADS  CAS  PubMed  Google Scholar 

  16. Schaltin, S., Vanhoutte, G., Wu, M., Bardé, F. & Fransaer, J. A QCM study of ORR-OER and an in situ study of a redox mediator in DMSO for Li-O2 batteries. Phys. Chem. Chem. Phys. 17, 12575–12586 (2015)

    Article  CAS  PubMed  Google Scholar 

  17. Das, U., Lau, K. C., Redfern, P. C. & Curtiss, L. A. Structure and stability of lithium superoxide clusters and relevance to Li–O2 batteries. J. Phys. Chem. Lett. 5, 813–819 (2014)

    Article  CAS  PubMed  Google Scholar 

  18. Sangster, J. & Pelton, A. D. The Li-O (lithium-oxygen) system. J. Phase Equilibria 13, 296–299 (1992)

    Article  CAS  Google Scholar 

  19. Lau, K. C., Curtiss, L. A. & Greeley, J. Density functional investigation of the thermodynamic stability of lithium oxide bulk crystalline structures as a function of oxygen pressure. J. Phys. Chem. C 115, 23625–23633 (2011)

    Article  CAS  Google Scholar 

  20. Kang, S., Mo, Y., Ong, S. P. & Ceder, G. A facile mechanism for recharging Li2O2 in Li–O2 batteries. Chem. Mater. 25, 3328–3336 (2013)

    Article  CAS  Google Scholar 

  21. Hummers, W. S. & Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339 (1958)

    Article  CAS  Google Scholar 

  22. Xu, Y., Sheng, K., Li, C. & Shi, G. Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano 4, 4324–4330 (2010)

    Article  CAS  PubMed  Google Scholar 

  23. Zhuravlev, Y. N. & Obolonskaya, O. S. Structure, mechanical stability, and chemical bond in alkali metal oxides. J. Struct. Chem. 51, 1005–1013 (2010)

    Article  CAS  Google Scholar 

  24. Kumar, S., Selvaraj, C., Munichandraiah, N. & Scanlon, L. G. Gold nanoparticles anchored reduced graphene oxide as catalyst for oxygen electrode of rechargeable Li-O2 cells. RSC Adv. 3, 21706–21714 (2013)

    Article  CAS  Google Scholar 

  25. Selvaraj, C., Kumar, S., Munichandraiah, N. & Scanlon, L. G. Reduced graphene oxide-polypyrrole composite as a catalyst for oxygen electrode of high rate rechargeable Li-O2 cells. J. Electrochem. Soc. 161, A554–A560 (2014)

    Article  CAS  Google Scholar 

  26. Oh, S. H., Black, R., Pomerantseva, E., Lee, J.-H. & Nazar, L. F. Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries. Nature Chem. 4, 1004–1010 (2012)

    Article  ADS  CAS  Google Scholar 

  27. Ren, X., Zhang, S. S., Tran, D. T. & Read, J. Oxygen reduction reaction catalyst on lithium/air battery discharge performance. J. Mater. Chem. 21, 10118–10125 (2011)

    Article  CAS  Google Scholar 

  28. Mitchell, R. R., Gallant, B. M., Shao-Horn, Y. & Thompson, C. V. Mechanisms of morphological evolution of Li2O2 particles during electrochemical growth. J. Phys. Chem. Lett. 4, 1060–1064 (2013)

    Article  CAS  PubMed  Google Scholar 

  29. Ottakam Thotiyl, M. M., Freunberger, S. A., Peng, Z. & Bruce, P. G. The carbon electrode in nonaqueous Li–O2 cells. J. Am. Chem. Soc. 135, 494–500 (2013)

    Article  CAS  PubMed  Google Scholar 

  30. Bikkarolla, S. K., Cumson, P., Joseph, P. & Papakonstantinou, P. Oxygen reduction reaction in electrochemically reduced graphene oxide. Faraday Discuss. 173, 415–428 (2014)

    Article  ADS  CAS  PubMed  Google Scholar 

  31. Antolini, E. Iridium as catalyst and cocatalyst for oxygen evolution/reduction in acidic polymer electrolyte membrane electrolyzers and fuel cells. ACS Catal. 4, 1426–1440 (2014)

    Article  CAS  Google Scholar 

  32. Donkersloot, H. C. & Van Vucht, J. H. N. The crystal structure of IrLi, Ir3Li and LiRh3 . J. Less Common Met. 50, 279–282 (1976)

    Article  CAS  Google Scholar 

  33. Pouget, E. M. et al. The initial stages of template-controlled CaCO3 formation revealed by cryo-TEM. Science 323, 1455–1458 (2009)

    Article  ADS  CAS  PubMed  Google Scholar 

  34. Ha, H.-W., Kim, I. Y., Hwang, S.-J. & Ruoff, R. S. One-pot synthesis of platinum nanoparticles embedded on reduced graphene oxide for oxygen reduction in methanol fuel cells. Electrochem. Solid-State Lett. 14, B70–B73 (2011)

    Article  CAS  Google Scholar 

  35. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996)

    Article  CAS  Google Scholar 

  36. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999)

    ADS  CAS  Google Scholar 

  37. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized Gradient Approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)

    ADS  CAS  PubMed  Google Scholar 

  38. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994)

    Article  ADS  Google Scholar 

  39. Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006)

    Article  CAS  PubMed  Google Scholar 

  40. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009)

    Article  PubMed  Google Scholar 

  41. Pickard, C. J. & Mauri, F. First-principles theory of the EPR g tensor in solids: defects in quartz. Phys. Rev. Lett. 88, 086403 (2002)

    Article  ADS  PubMed  Google Scholar 

  42. Ziegler, M., Rosenfeld, M., Kaenzig, W. & Fischer, P. Strukturuntersuchungen an Alkalihyperoxiden. Helvetica Physica Acta 49, 57–90 (1976)

    CAS  Google Scholar 

  43. Adrian, F. J., Cochran, E. L. & Bowers, V. A. ESR spectra and structures of NaSO2 and NaO2 . J. Chem. Phys. 59, 56–60 (1973)

    Article  ADS  CAS  Google Scholar 

  44. Lindsay, D. M. & Garland, D. A. ESR spectra of matrix-isolated lithium superoxide. J. Phys. Chem. 91, 6158–6161 (1987)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

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

  1. Jun Lu, Yun Jung Lee, Xiangyi Luo, Kah Chun Lau and Mohammad Asadi: These authors contributed equally to this work.

Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, 60439, Illinois, 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, 60439, Illinois, 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, 84112, Utah, USA

    Xiangyi Luo & Zhigang Zak Fang

  5. Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, 60607, Illinois, USA

    Mohammad Asadi & Amin Salehi-Khojin

  6. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Jianguo Wen & Dean J. Miller

  7. Conn Center for Renewable Energy Research, University of Louisville, Louisville, 40292, Kentucky, USA

    Bijandra Kumar

Authors
  1. Jun Lu
    View author publications

    You can also search for this author inPubMed Google Scholar

  2. Yun Jung Lee
    View author publications

    You can also search for this author inPubMed Google Scholar

  3. Xiangyi Luo
    View author publications

    You can also search for this author inPubMed Google Scholar

  4. Kah Chun Lau
    View author publications

    You can also search for this author inPubMed Google Scholar

  5. Mohammad Asadi
    View author publications

    You can also search for this author inPubMed Google Scholar

  6. Hsien-Hau Wang
    View author publications

    You can also search for this author inPubMed Google Scholar

  7. Scott Brombosz
    View author publications

    You can also search for this author inPubMed Google Scholar

  8. Jianguo Wen
    View author publications

    You can also search for this author inPubMed Google Scholar

  9. Dengyun Zhai
    View author publications

    You can also search for this author inPubMed Google Scholar

  10. Zonghai Chen
    View author publications

    You can also search for this author inPubMed Google Scholar

  11. Dean J. Miller
    View author publications

    You can also search for this author inPubMed Google Scholar

  12. Yo Sub Jeong
    View author publications

    You can also search for this author inPubMed Google Scholar

  13. Jin-Bum Park
    View author publications

    You can also search for this author inPubMed Google Scholar

  14. Zhigang Zak Fang
    View author publications

    You can also search for this author inPubMed Google Scholar

  15. Bijandra Kumar
    View author publications

    You can also search for this author inPubMed Google Scholar

  16. Amin Salehi-Khojin
    View author publications

    You can also search for this author inPubMed Google Scholar

  17. Yang-Kook Sun
    View author publications

    You can also search for this author inPubMed Google Scholar

  18. Larry A. Curtiss
    View author publications

    You can also search for this author inPubMed Google Scholar

  19. Khalil Amine
    View author publications

    You can also search for this author inPubMed Google Scholar

Contributions

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.

Corresponding authors

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

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

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

Supplementary Information

This file contains Supplementary Figures 1-18, Supplementary Tables 1-3 and Supplementary References. (PDF 3650 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lu, J., Jung Lee, Y., Luo, X. et al. A lithium–oxygen battery based on lithium superoxide. Nature 529, 377–382 (2016). https://doi.org/10.1038/nature16484

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature16484

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing