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Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

Nature Energy volume 2, Article number: 17012 (2017) Cite this article

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Abstract

Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI–LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75 mAh cm−2, a cyclability of 97.1% capacity retention after 500 cycles along with very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm−2. The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.

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Figure 1: Electrochemical behaviour of Li||NMC batteries using different carbonate-based electrolytes.
Figure 2: Rate performance of Li||NMC batteries using various electrolytes at 30 ∘C.
Figure 3: Effects of additive content and testing conditions.
Figure 4: Morphological and interfacial evolution of Li metal anodes.
Figure 5: Characterization of the components of SEI produced on cycled Li metal anodes.
Figure 6: Molecular orbital energies and evolution of SEI layer compositions.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program under contract no. DE-AC02-05CH11231. W.X. also thanks the Battery500 Consortium for the partial support through the BMR Program. Microscopy as well as spectroscopy characterizations were performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a National Scientific User Facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the DOE under contract no. DE-AC05-76RLO1830. The NMC electrodes were produced at the US DOE’s CAMP Facility, ANL. The CAMP Facility is fully supported by the DOE VTO within the core funding of the Applied Battery Research (ABR) for Transportation Program.

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Authors and Affiliations

  1. Energy and Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, USA

    Jianming Zheng, Shuhong Jiao, Ji-Guang Zhang & Wu Xu

  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 3335 Innovation Boulevard, Richland, Washington 99354, USA

    Mark H. Engelhard

  3. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, USA

    Donghai Mei

  4. Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA

    Bryant J. Polzin

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  1. Jianming Zheng
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Contributions

J.Z., W.X. and J.-G.Z. initiated this research and designed the experiments. B.J.P. prepared and provided the standard NMC electrodes. J.Z. performed the electrochemical measurements with assistance from S.J., as well as the SEM observations. M.H.E. and D.M. performed XPS measurements and molecular dynamics simulations, respectively. J.Z., J.-G.Z., and W.X. prepared this manuscript with input from other co-authors.

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Correspondence to Ji-Guang Zhang or Wu Xu.

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The authors declare no competing financial interests.

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Supplementary Information

Supplementary Figures 1–14, Supplementary Table 1, Supplementary References. (PDF 1940 kb)

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Zheng, J., Engelhard, M., Mei, D. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat Energy 2, 17012 (2017). https://doi.org/10.1038/nenergy.2017.12

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