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Anion-redox nanolithia cathodes for Li-ion batteries

Nature Energy volume 1, Article number: 16111 (2016) Cite this article

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Abstract

The development of lithium–air batteries is plagued by a high potential gap (>1.2 V) between charge and discharge, and poor cyclability due to the drastic phase change of O2 (gas) and Ox− (condensed phase) at the cathode during battery operations. Here we report a cathode consisting of nanoscale amorphous lithia (nanolithia) confined in a cobalt oxide, enabling charge/discharge between solid Li2O/Li2O2/LiO2 without any gas evolution. The cathode has a theoretical capacity of 1,341 Ah kg−1, a mass density exceeding 2.2 g cm−3, and a practical discharge capacity of 587 Ah kg−1 at 2.55 V versus Li/Li+. It also displays stable cycling performance (only 1.8% loss after 130 cycles in lithium-matched full-cell tests against Li4Ti5O12 anode), as well as a round-trip overpotential of only 0.24 V. Interestingly, the cathode is automatically protected from O2 gas release and overcharging through the shuttling of self-generated radical species soluble in the carbonate electrolyte.

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Figure 1: The structure and electrochemical performance of nanolithia cathode.
Figure 2: The transformation of nanolithia during electrochemical cycling.
Figure 3: Battery overcharge protection by electrolyte shuttling.
Figure 4: Electrochemical performance of lithium-matched full-cell battery.

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Acknowledgements

We acknowledge financial support by NSF DMR-1410636. We thank Z. Wang for assistance with TEM measurements and analysis. We also thank H. Yao for help with the NMR data analysis and layout of the figures. This work was also partially supported by the US Department of Energy under Contract DE-AC0206CH11357 from the Vehicle Technologies Office, Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE).

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Authors and Affiliations

  1. Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Zhi Zhu, Akihiro Kushima, Zongyou Yin & Ju Li

  2. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Zhi Zhu, Akihiro Kushima, Zongyou Yin & Ju Li

  3. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

    Lu Qi

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

    Khalil Amine & Jun Lu

Authors
  1. Zhi Zhu
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  4. Lu Qi
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Contributions

J.Li and Z.Z. conceived the original idea of this paper. Z.Z. performed the material synthesis and measurements, and then improved the experiments after discussions with J.Li and J.Lu. Z.Y. assisted with the Raman and XPS experiments; A.K. performed the TEM experiments and NMR calculation. Z.Z. and J.Li drafted the paper, and all authors revised it. L.Q. and K.A. provided many suggestions and guidance.

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Correspondence to Lu Qi, Jun Lu or Ju Li.

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The authors declare no competing financial interests.

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Supplementary Figures 1–9, Supplementary References (PDF 817 kb)

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Zhu, Z., Kushima, A., Yin, Z. et al. Anion-redox nanolithia cathodes for Li-ion batteries. Nat Energy 1, 16111 (2016). https://doi.org/10.1038/nenergy.2016.111

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