Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

  • Nature Energy 2, Article number: 17012 (2017)
  • doi:10.1038/nenergy.2017.12
  • Download Citation
Published online:


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.

  • Subscribe to Nature Energy for full access:



  • Purchase article full text and PDF:


    Buy now

Additional access options:

Already a subscriber?  Log in  now or  Register  for online access.


  1. 1.

    ,  & Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014).

  2. 2.

    et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

  3. 3.

    et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat. Energy 1, 16010 (2016).

  4. 4.

    et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotech. 11, 626–632 (2016).

  5. 5.

    , ,  & Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 136, 7395–7402 (2014).

  6. 6.

    et al. SiO2 Hollow nanosphere-based composite solid electrolyte for lithium metal batteries to suppress lithium dendrite growth and enhance cycle life. Adv. Energy Mater. 6, 201502214 (2016).

  7. 7.

    , ,  & A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 6, 10101 (2015).

  8. 8.

    ,  & Stabilizing lithium metal using ionic liquids for long-lived batteries. Nat. Commun. 7, 11794 (2016).

  9. 9.

    , ,  & Application of the N-propyl-N-methyl-pyrrolidinium bis(fluorosulfonyl)imide RTIL containing lithium bis(fluorosulfonyl)imide in ionic liquid based lithium batteries. J. Electrochem. Soc. 157, A66–A74 (2010).

  10. 10.

    , ,  & Extensive charge–discharge cycling of lithium metal electrodes achieved using ionic liquid electrolytes. Electrochem. Commun. 27, 69–72 (2013).

  11. 11.

    et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 135, 4450–4456 (2013).

  12. 12.

    et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

  13. 13.

    , ,  & An artificial solid electrolyte interphase layer for stable lithium metal anodes. Adv. Mater. 28, 1853–1858 (2016).

  14. 14.

    ,  & Improved cycle life and stability of lithium metal anodes through ultrathin atomic layer deposition surface treatments. Chem. Mater. 27, 6457–6462 (2015).

  15. 15.

    et al. Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode. Nano Lett. 14, 6016–6022 (2014).

  16. 16.

    et al. Dendrite-free lithium deposition induced by uniformly distributed lithium ions for efficient lithium metal batteries. Adv. Mater. 28, 2888–2895 (2016).

  17. 17.

    et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotech. 9, 618–623 (2014).

  18. 18.

    et al. Highly stable operation of lithium metal batteries enabled by the formation of a transient high-concentration electrolyte layer. Adv. Energy Mater. 6, 201502151 (2016).

  19. 19.

    et al. Failure mechanism for fast-charged lithium metal batteries with liquid electrolytes. Adv. Energy Mater. 5, 1400993 (2015).

  20. 20.

    et al. Enhanced charging capability of lithium metal batteries based on lithium bis(trifluoromethanesulfonyl)imide-lithium bis(oxalato)borate dual-salt electrolytes. J. Power Sources 318, 170–177 (2016).

  21. 21.

    et al. Effects of carbonate solvents and lithium salts on morphology and coulombic efficiency of lithium electrode. J. Electrochem. Soc. 160, A1894–A1901 (2013).

  22. 22.

    , ,  & Analysis of vinylene carbonate derived SEI layers on graphite anode. J. Electrochem. Soc. 151, A1659–A1669 (2004).

  23. 23.

    , ,  & Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes. J. Power Sources 189, 1132–1140 (2009).

  24. 24.

    et al. On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries. Electrochim. Acta 47, 1423–1439 (2002).

  25. 25.

    et al. Characterization of lithium alkyl carbonates by X-ray photoelectron spectroscopy: experimental and theoretical study. J. Phys. Chem. B 109, 15868–15875 (2005).

  26. 26.

    , ,  & XPS analysis of the SEI formed on carbonaceous materials. Solid State Ion. 170, 83–91 (2004).

  27. 27.

    Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4418 (2004).

  28. 28.

    , , ,  & Chemical reactivity of PF5 and LiPF6 in ethylene carbonate/dimethyl carbonate solutions. Electrochem. Solid-State Lett. 4, A42–A44 (2001).

  29. 29.

    et al. Gaussian 09 (Gaussian, 2009).

  30. 30.

     & The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol. Phys. 19, 553–566 (1970).

  31. 31.

    ,  & Development of the Colle–Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988).

Download references


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.

Author information


  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


  1. Search for Jianming Zheng in:

  2. Search for Mark H. Engelhard in:

  3. Search for Donghai Mei in:

  4. Search for Shuhong Jiao in:

  5. Search for Bryant J. Polzin in:

  6. Search for Ji-Guang Zhang in:

  7. Search for Wu Xu in:


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.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Ji-Guang Zhang or Wu Xu.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    Supplementary Figures 1–14, Supplementary Table 1, Supplementary References.