Rechargeable-battery chemistry based on lithium oxide growth through nitrate anion redox

Abstract

Next-generation lithium-battery cathodes often involve the growth of lithium-rich phases, which enable specific capacities that are 2−3 times higher than insertion cathode materials, such as lithium cobalt oxide. Here, we investigated battery chemistry previously deemed irreversible in which lithium oxide, a lithium-rich phase, grows through the reduction of the nitrate anion in a lithium nitrate-based molten salt at 150 °C. Using a suite of independent characterization techniques, we demonstrated that a Ni nanoparticle catalyst enables the reversible growth and dissolution of micrometre-sized lithium oxide crystals through the effective catalysis of nitrate reduction and nitrite oxidation, which results in high cathode areal capacities (~12 mAh cm–2). These results enable a rechargeable battery system that has a full-cell theoretical specific energy of 1,579 Wh kg–1, in which a molten nitrate salt serves as both an active material and the electrolyte.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Electrochemical reduction of nitrate anions and reversible formation of Li2O discharge product.
Fig. 2: Elucidation and characterization of battery discharge and charge mechanisms.
Fig. 3: The cathode surface catalysis promotes reversible nitrate electrochemistry.
Fig. 4: Molten nitrate cell using Ni nanocatalyst with a long cycle life.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

References

  1. 1.

    Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    CAS  Article  Google Scholar 

  2. 2.

    McCloskey, B. D., Burke, C. M., Nichols, J. E. & Renfrew, S. E. Mechanistic insights for the development of Li–O2 battery materials: addressing Li2O2 conductivity limitations and electrolyte and cathode instabilities. Chem. Commun. 51, 12701–12715 (2015).

    CAS  Article  Google Scholar 

  3. 3.

    Abraham, K. M. & Jiang, Z. A polymer electrolyte-based rechargeable lithium/oxygen battery. J. Electrochem. Soc. 143, 1–5 (1996).

    CAS  Article  Google Scholar 

  4. 4.

    Aurbach, D., McCloskey, B. D., Nazar, L. F. & Bruce, P. G. Advances in understanding mechanisms underpinning lithium–air batteries. Nat. Energy 1, 1–11 (2016).

    Article  Google Scholar 

  5. 5.

    Yamin, H. & Peled, E. Electrochemistry of a nonaqueous lithium/sulfur cell. J. Power Sources 9, 281–287 (1983).

    CAS  Article  Google Scholar 

  6. 6.

    Pang, Q., Liang, X., Kwok, C. Y. & Nazar, L. F. Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes. Nat. Energy 1, 1–11 (2016).

    Article  Google Scholar 

  7. 7.

    Raistrick, I. D., Poris, J. & Huggins, R. A. in Proc. Symposium on Lithium Batteries Vol. 81(4) (ed. Venkatssety, H. V.) 477–483 (The Electrochemical Society, 1981).

  8. 8.

    Miles, M. H. Cation effects on the electrode reduction of molten nitrates. J. Electrochem. Soc. 127, 1761–1766 (1980).

    CAS  Article  Google Scholar 

  9. 9.

    Desimoni, E., Palmisano, F. & Zambonin, P. G. Catalytic currents in fused salts: discharge mechanism of nitrite in molten alkali nitrates. J. Electroanal. Chem. 84, 315–322 (1977).

    CAS  Article  Google Scholar 

  10. 10.

    Huggins, R. Advanced Batteries: Materials Science Aspects (Springer Science & Business Media, 2008).

  11. 11.

    Addison, D. D. et al. Rechargeable batteries employing catalyzed molten nitrate positive electrodes. US patent 2016/0204418 A1 (2016).

  12. 12.

    Seriani, N. Ab initio thermodynamics of lithium oxides: from bulk phases to nanoparticles. Nanotechnology 20, 445703 (2009).

    Article  Google Scholar 

  13. 13.

    Giordani, V. et al. A molten salt lithium–oxygen battery. J. Am. Chem. Soc. 138, 2656–2663 (2016).

    CAS  Article  Google Scholar 

  14. 14.

    Xia, C. et al. A high-energy-density lithium–oxygen battery based on a reversible four-electron conversion to lithium oxide. Science 361, 777–781 (2018).

    CAS  Article  Google Scholar 

  15. 15.

    James, D. W. & Leong, W. H. Structure of molten nitrates. III. Vibrational spectra of LiNO3, NaNO3, and AgNO3. J. Chem. Phys. 51, 640–646 (1969).

    CAS  Article  Google Scholar 

  16. 16.

    Balasubrahmanyam, K. & Janz, G. J. Molten mixtures of AgNO3 and TlNO3: Raman spectra and structure. J. Chem. Phys. 57, 4089–4091 (1972).

    CAS  Article  Google Scholar 

  17. 17.

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

    CAS  Article  Google Scholar 

  18. 18.

    McCloskey, B. D. et al. Twin problems of interfacial carbonate formation in nonaqueous Li–O2 batteries. J. Phys. Chem. Lett. 3, 997–1001 (2012).

    CAS  Article  Google Scholar 

  19. 19.

    Chiang, Y.-M., Birnie, D. P., Kingery, W. D. & Newcomb, S. Physical Ceramics: Principles for Ceramic Science and Engineering (Wiley, 1997).

  20. 20.

    Tenent, R. C. et al. Fast-switching electrochromic Li+-doped NiO films by ultrasonic spray deposition. J. Electrochem. Soc. 157, H318–H322 (2010).

    CAS  Article  Google Scholar 

  21. 21.

    Chia-Ching, W. & Cheng-Fu, Y. Investigation of the properties of nanostructured Li-doped NiO films using the modified spray pyrolysis method. Nanoscale Res. Lett. 8, 1–5 (2013).

    Article  Google Scholar 

  22. 22.

    Nguyen, Q. M. Technological status of nickel oxide cathodes in molten carbonate fuel cells—a review. J. Power Sources 24, 1–19 (1988).

    Article  Google Scholar 

  23. 23.

    Desimoni, E., Paniccia, F. & Zambonin, P. G. Solubility and detection (down to 30 p.p.b.) of oxygen in molten alkali nitrates. J. Electroanal. Chem. 38, 373–379 (1972).

    CAS  Article  Google Scholar 

  24. 24.

    Gallant, B. M. et al. Chemical and morphological changes of Li–O2 battery electrodes upon cycling. J. Phys. Chem. C 116, 20800–20805 (2012).

    CAS  Article  Google Scholar 

  25. 25.

    Freunberger, S. A. et al. Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 133, 8040–8047 (2011).

    CAS  Article  Google Scholar 

  26. 26.

    Kwabi, D. G. et al. Chemical instability of dimethyl sulfoxide in lithium–air batteries. J. Phys. Chem. Lett. 5, 2850–2856 (2014).

    CAS  Article  Google Scholar 

  27. 27.

    Giordani, V. et al. Efficient Rechargeable Li/O 2 Batteries Utilizing Stable Inorganic Molten Salt Electrolytes 2016 (DOE Vehicle Technologies Program Review, 2016); www.energy.gov/sites/prod/files/2016/06/f32/es233_giordani_2016_p_web.pdf

Download references

Acknowledgements

We thank C. Garland for assistance with the TEM operation, N. Dalleska and the Environmental Analysis Center of the California Institute of Technology for assistance with the ion exchange chromatography, K. Narita for assistance collecting Raman spectra and the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology for use of their XPS. This work was supported by the FY 2014 Vehicle Technologies Program Wide Funding Opportunity Announcement, under Award no. DE-FOA-0000991 (0991–1872), by the US Department of Energy (DOE) and National Energy Technology Laboratory (NETL) on behalf of the Office of Energy Efficiency and Renewable Energy (EERE).

Author information

Affiliations

Authors

Contributions

D.A., G.V.C., V.G. and J.U. conceived the project. V.G., J.U., D.T. and H.T. collected the electrochemical data. D.T. performed the electron microscopy, diffraction and chromatography. H.T. performed the Raman spectroscopy. D.T. and B.M.G. performed the XPS. J.U. performed the ultraviolet–visible spectroscopy and synthesized Li-doped Ni oxide. B.D.M. and J.R.G. assisted with the data analysis. D.T. and V.G. wrote the manuscript with input from all the authors.

Corresponding authors

Correspondence to Vincent Giordani or Dan Addison.

Ethics declarations

Competing interests

D.A., G.V.C., V.G. and J.U. are inventors on US patent application 2016/0204418.

Additional information

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

Supplementary information

Supplementary information

Supplementary Figs. 1–12, Supplementary Table 1 and Supplementary Characterization.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Giordani, V., Tozier, D., Uddin, J. et al. Rechargeable-battery chemistry based on lithium oxide growth through nitrate anion redox. Nat. Chem. 11, 1133–1138 (2019). https://doi.org/10.1038/s41557-019-0342-6

Download citation

Further reading

Search

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