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.

A lithium–oxygen battery with a long cycle life in an air-like atmosphere

Nature volume 555, pages 502–506 (2018)Cite this article

Subjects

Abstract

Lithium–air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy1. So far, however, such systems have been largely restricted to pure oxygen environments (lithium–oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte2,3,4,5. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex6,7,8,9,10,11. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium–oxygen systems may be too small for practical applications12. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode2 and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium–air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium–oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

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

Figure 1: Characterization of the protected anode.
Figure 2: Performance of the cathode in a lithium–air battery system.
Figure 3: Electron microscopy of the cathode.
Figure 4: Computational study of the anode, cathode and electrolyte of the lithium–air battery cell.

References

  1. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012)

    ADS  CAS  Google Scholar 

  2. Asadi, M. et al. Cathode based on molybdenum disulfide nanoflakes for lithium–oxygen batteries. ACS Nano 10, 2167–2175 (2016)

    Article  CAS  Google Scholar 

  3. Jung, H.-G., Hassoun, J., Park, J.-B., Sun, Y.-K. & Scrosati, B. An improved high-performance lithium–air battery. Nat. Chem. 4, 579–585 (2012)

    Article  CAS  Google Scholar 

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

    Article  ADS  Google Scholar 

  5. Assary, R. S. et al. The effect of oxygen crossover on the anode of a Li–O2 battery using an ether-based solvent: insights from experimental and computational studies. ChemSusChem 6, 51–55 (2013)

    Article  CAS  Google Scholar 

  6. Geng, D. et al. From lithium–oxygen to lithium–air batteries: challenges and opportunities. Adv. Energy Mater. 6, 1502164 (2016)

    Article  Google Scholar 

  7. Christensen, J. et al. A critical review of Li/air batteries. J. Electrochem. Soc. 159, R1–R30 (2012)

    Article  CAS  Google Scholar 

  8. Garcia-Araez, N. & Novák, P. Critical aspects in the development of lithium–air batteries. J. Solid State Electrochem. 17, 1793–1807 (2013)

    Article  CAS  Google Scholar 

  9. Zhang, T. & Zhou, H. A reversible long-life lithium–air battery in ambient air. Nat. Commun. 4, 1817 (2013)

    Article  ADS  Google Scholar 

  10. Das, S. K., Chai, J., Rahman, S. & Sarkar, A. Synthesis, characterization and performance evaluation of an advanced solid electrolyte and air cathode for rechargeable lithium–air batteries. J. Mater. Sci. Chem. Eng. 4, 74–89 (2016)

    CAS  Google Scholar 

  11. Wu, S. et al. A synergistic system for lithium–oxygen batteries in humid atmosphere integrating a composite cathode and a hydrophobic ionic liquid-based electrolyte. Adv. Funct. Mater. 26, 3291–3298 (2016)

    Article  CAS  Google Scholar 

  12. Gallagher, K. G. et al. Quantifying the promise of lithium–air batteries for electric vehicles. Energy Environ. Sci. 7, 1555–1563 (2014)

    Article  CAS  Google Scholar 

  13. Pasierb, P., Komornicki, S., Rokita, M. & Rȩkas, M. Structural properties of Li2CO3–BaCO3 system derived from IR and Raman spectroscopy. J. Mol. Struct. 596, 151–156 (2001)

    Article  ADS  CAS  Google Scholar 

  14. Bi, Y. et al. Stability of Li2CO3 in cathode of lithium ion battery and its influence on electrochemical performance. RSC Advances 6, 19233–19237 (2016)

    Article  CAS  Google Scholar 

  15. Sina, M. et al. Investigation of SEI layer formation in conversion iron fluoride cathodes by combined STEM/EELS and XPS. J. Phys. Chem. C 119, 9762–9773 (2015)

    Article  CAS  Google Scholar 

  16. Imanishi, N., Luntz, A. C. & Bruce, P. (eds) The Lithium Air Battery: Fundamentals (Springer, 2014)

  17. Du, P. et al. Compatibility of lithium salts with solvent of the non-aqueous electrolyte in Li–O2 batteries. Phys. Chem. Chem. Phys. 15, 5572–5581 (2013)

    Article  CAS  Google Scholar 

  18. Lu, Y.-C. et al. In situ ambient pressure X-ray photoelectron spectroscopy studies of lithium–oxygen redox reactions. Sci. Rep. 2, 715 (2012)

    Article  Google Scholar 

  19. McCloskey, B. D., Bethune, D. S., Shelby, R. M., Girishkumar, G. & Luntz, A. C. Solvents’ critical role in nonaqueous lithium–oxygen battery. J. Phys. Chem. Lett. 2, 1161–1166 (2011)

    Article  CAS  Google Scholar 

  20. Lu, J. et al. A lithium–oxygen battery based on lithium superoxide. Nature 529, 377–382 (2016)

    Article  ADS  CAS  Google Scholar 

  21. Leung, K., Soto, F., Hankins, K., Balbuena, P. B. & Harrison, K. L. Stability of solid electrolyte interphase components on lithium metal and reactive anode material surfaces. J. Phys. Chem. C 120, 6302–6313 (2016)

    Article  CAS  Google Scholar 

  22. Iddir, H. & Curtiss, L. A. Li ion diffusion mechanisms in bulk monoclinic Li2CO3 crystals from density functional. J. Phys. Chem. C 114, 20903–20906 (2010)

    Article  CAS  Google Scholar 

  23. Shi, S., Qi, Y., Li, H. & Hector, L. G. Defect thermodynamics and diffusion mechanisms in Li2CO3 and implications for the solid electrolyte interphase in Li-ion batteries. J. Phys. Chem. C 117, 8579–8593 (2013)

    Article  CAS  Google Scholar 

  24. Cheng, L. et al. Computational studies of solubilities of LiO2 and Li2O2 in aprotic solvents. J. Electrochem. Soc. 164, E3696–E3701 (2017)

    Article  CAS  Google Scholar 

  25. Johnson, L. et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nat. Chem. 6, 1091–1099 (2014)

    Article  CAS  Google Scholar 

  26. Welland, M. J. et al. An atomistically informed mesoscale model for growth and coarsening during discharge in lithium–oxygen batteries. J. Chem. Phys. 143, 224113 (2015)

    Article  ADS  Google Scholar 

  27. Adams, B. D. et al. Current density dependence of peroxide formation in the Li–O2 battery and its effect on charge. Energy Environ. Sci. 6, 1772 (2013)

    Article  CAS  Google Scholar 

  28. Xiao, D. et al. Direct observation of ordered oxygen defects on the atomic scale in Li2O2 for Li–O2 batteries. Adv. Energy Mater. 5, 1400664 (2015)

    Article  Google Scholar 

  29. 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 

  30. 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 

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

    Article  ADS  CAS  Google Scholar 

  32. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)

    Article  ADS  CAS  Google Scholar 

  33. Frisch, M. J. et al. Gaussian 09, Revision D.01. (Gaussian Inc., 2009)

  34. Berendsen, H. J. C., van der Spoel, D. & van Drunen, R. GROMACS: A message-passing parallel molecular dynamics implementation. Comput. Phys. Commun. 91, 43–56 (1995)

    Article  ADS  CAS  Google Scholar 

  35. Abraham, M. J. et al. GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 1–2, 19–25 (2015)

    Article  ADS  Google Scholar 

  36. Horta, B. A. C. et al. A GROMOS-compatible force field for small organic molecules in the condensed phase: the 2016H66 parameter set. J. Chem. Theory Comput. 12, 3825–3850 (2016)

    Article  CAS  Google Scholar 

  37. Berendsen, H. J. C. et al. in Intermolecular Forces Vol. 14 (ed. Pullman, B. ) 331–342 (Springer, 1981)

    Book  Google Scholar 

  38. Berendsen, H. J. C., Grigera, J. R. & Straatsma, T. P. The missing term in effective pair potentials. J. Phys. Chem. 91, 6269–6271 (1987)

    Article  CAS  Google Scholar 

  39. Mark, P. & Nilsson, L. Structure and dynamics of liquid water with different long-range interaction truncation and temperature control methods in molecular dynamics simulations. J. Comput. Chem. 23, 1211–1219 (2002)

    Article  CAS  Google Scholar 

  40. Mark, P. & Nilsson, L. Structure and dynamics of the TIP3P, SPC, and SPC/E water models at 298 K. J. Phys. Chem. A 105, 9954–9960 (2001)

    Article  CAS  Google Scholar 

  41. Berendsen, H. J. C., Postma, J. P. M., van Gunsteren, W. F., DiNola, A. & Haak, J. R. Molecular dynamics with coupling to an external bath. J. Chem. Phys. 81, 3684–3690 (1984)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

The work of A.S.-K., M. A., B. S. and P. A. was supported by the National Science Foundation (NSF-DMREF Award #1729420). Work by B.N., K.C.L., R.S.A., L.A.C., R.F.K., A.M., X. H. and J.R.J. was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences. Work by A.N. and C.L. was supported by the Center for Electrical Energy Storage: Tailored Interfaces, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. The work of F.K.A. and K.K. was supported by a University of Illinois at Chicago start-up fund. C.L. was also supported by programme development funds provided by the Chemical Sciences and Engineering division at Argonne National Laboratory. We acknowledge the MRSEC Materials Preparation and Measurement Laboratory shared user facility at the University of Chicago (NSFDMR-1420709); the EPIC facility (NUANCE Center, Northwestern University), which has received support from the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the Nanoscale Science and Engineering Center (NSF EEC−0647560) at the International Institute for Nanotechnology; and the State of Illinois, through the International Institute for Nanotechnology. This work also made use of the Integrated Molecular Structure Education and Research Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205). The acquisition of the UIC JEOL JEM ARM200CF was supported by an MRI-R2 grant from the National Science Foundation (DMR-0959470). The use of instrumentation at University of Illinois at Chicago Research Resources Center (RRC-East) is acknowledged. A. Nicholls at UIC’s Electron Microscopy Service is also acknowledged for help and support. This research used high performance computing resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract DE-AC02-06CH11357. F.K.A. acknowledges the use of the University of Illinois at Chicago High Performance Computing Cluster to perform molecular dynamics simulations. We thank K. Gallagher, P. Redfern, H.-H. Wang, J. Jureller and X. Chen.

Author information

Authors and Affiliations

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

    Mohammad Asadi, Baharak Sayahpour, Pedram Abbasi, Marc Gerard, Poya Yasaei & Amin Salehi-Khojin

  2. Department of Chemical and Biological Engineering, Illinois Institute of Technology, Chicago, 60616, Illinois, USA

    Mohammad Asadi

  3. Materials Science Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Anh T. Ngo, Badri Narayanan, Rajeev S. Assary & Larry A. Curtiss

  4. Department of Physics, University of Illinois at Chicago, Chicago, 60607, Illinois, USA

    Klas Karis, Jacob R. Jokisaari, Xuan Hu, Arijita Mukherjee, Fatemeh Khalili-Araghi & Robert F. Klie

  5. Chemical Sciences Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Cong Liu

  6. Department of Physics and Astronomy, California State University, Northridge, 91330, California, USA

    Kah Chun Lau

Authors
  1. Mohammad Asadi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Baharak Sayahpour
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pedram Abbasi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anh T. Ngo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Klas Karis
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jacob R. Jokisaari
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Cong Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Badri Narayanan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Marc Gerard
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Poya Yasaei
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Xuan Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Arijita Mukherjee
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Kah Chun Lau
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Rajeev S. Assary
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Fatemeh Khalili-Araghi
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Robert F. Klie
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Larry A. Curtiss
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Amin Salehi-Khojin
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.S.-K. and M.A. conceived the idea. M.A., B.S., P.A. and M.G. performed the electrochemical experiments. M.A. and B.S. synthesized the MoS2 nanoflakes. M.A., B.S., P.A. and P.Y. carried out characterization. A.S.-K. supervised the electrochemical experiments. B.N., K.C.L., R.S.A. and L.A.C. carried out the computational studies of electrolytes. C.L. and A.T.N. performed computational studies of surfaces and the Li2CO3 coating. J.R.J., X.H., A.M. and R.F.K. carried out STEM and EELS experiments. K.K. and F.K.-A. performed classical molecular dynamics simulations. All of the authors contributed to the manuscript before submission.

Corresponding authors

Correspondence to Larry A. Curtiss or Amin Salehi-Khojin.

Ethics declarations

Competing interests

A.S.-K., M.A., B.S. and P.A. have filed a provisional patent application. The other authors declare no competing interests.

Additional information

Reviewer Information Nature thanks S. Soon, G. Yu and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

This file contains Supplementary Text and Data, Supplementary Figures 1-50, Supplementary Tables 1-6 and Supplementary References – see contents page for details. (PDF 5646 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Asadi, M., Sayahpour, B., Abbasi, P. et al. A lithium–oxygen battery with a long cycle life in an air-like atmosphere. Nature 555, 502–506 (2018). https://doi.org/10.1038/nature25984

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature25984

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

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