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Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries

Nature Chemistry volume 7, pages 50–56 (2015)Cite this article

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Abstract

Given their high theoretical specific energy, lithium–oxygen batteries have received enormous attention as possible alternatives to current state-of-the-art rechargeable Li–ion batteries. However, the maximum discharge capacity in non-aqueous lithium–oxygen batteries is limited to a small fraction of its theoretical value due to the build-up of insulating lithium peroxide (Li2O2), the battery’s primary discharge product. The discharge capacity can be increased if Li2O2 forms as large toroidal particles rather than as a thin conformal layer. Here, we show that trace amounts of electrolyte additives, such as H2O, enhance the formation of Li2O2 toroids and result in significant improvements in capacity. Our experimental observations and a growth model show that the solvating properties of the additives prompt a solution-based mechanism that is responsible for the growth of Li2O2 toroids. We present a general formalism describing an additive’s tendency to trigger the solution process, providing a rational design route for electrolytes that afford larger lithium–oxygen battery capacities.

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Figure 1: Li2O2 discharge product morphology control.
Figure 2: Discharge capacity increase with increasing water content in the electrolyte.
Figure 3: Ex situ XRD measurements on discharged cathodes.
Figure 4: The two pathways for Li2O2 formation.
Figure 5: Proposed mechanism for the growth of Li2O2 toroids in the presence of water.
Figure 6: Quantitative basis for solvent selection for high-capacity Li–O2 batteries.

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Acknowledgements

The authors thank R. Shelby for Raman measurements, D. Bethune and G. Wallraff for discussions and help with experiments and the IBM model shop for support with the DEMS system. N.B.A. acknowledges guidance from H.C. Kim and W.W. Wilcke. V.V. is supported by a faculty startup grant from Carnegie Mellon University.

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Authors and Affiliations

  1. IBM Almaden Research Center, San Jose, 95120, California, USA

    Nagaphani B. Aetukuri, Bryan D. McCloskey, Jeannette M. García, Leslie E. Krupp & Alan C. Luntz

  2. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, 94720, California, USA

    Bryan D. McCloskey

  3. Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California

    Bryan D. McCloskey

  4. Department of Mechanical Engineering, Carnegie Mellon University, Pittsburgh, 15213, Pennsylvania, USA

    Venkatasubramanian Viswanathan

  5. SUNCAT, SLAC National Accelerator Laboratory, Menlo Park, 94025, California, USA

    Alan C. Luntz

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  1. Nagaphani B. Aetukuri
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  3. Jeannette M. García
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  4. Leslie E. Krupp
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  5. Venkatasubramanian Viswanathan
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Contributions

All authors contributed to the design of the research. N.B.A., J.M.G. and L.E.K. performed the experimental measurements and N.B.A. performed the experimental data analysis. V.V. and A.C.L. designed the theoretical calculations, which V.V. then performed. N.B.A., B.D.M., V.V. and A.C.L. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Nagaphani B. Aetukuri or Venkatasubramanian Viswanathan.

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The authors declare no competing financial interests.

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Aetukuri, N., McCloskey, B., García, J. et al. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nature Chem 7, 50–56 (2015). https://doi.org/10.1038/nchem.2132

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