Glassy Li metal anode for high-performance rechargeable Li batteries


Lithium metal has been considered an ideal anode for high-energy rechargeable Li batteries, although its nucleation and growth process remains mysterious, especially at the nanoscale. Here, cryogenic transmission electron microscopy was used to reveal the evolving nanostructure of Li metal deposits at various transient states in the nucleation and growth process, in which a disorder–order phase transition was observed as a function of current density and deposition time. The atomic interaction over wide spatial and temporal scales was depicted by reactive molecular dynamics simulations to assist in understanding the kinetics. Compared to crystalline Li, glassy Li outperforms in electrochemical reversibility, and it has a desired structure for high-energy rechargeable Li batteries. Our findings correlate the crystallinity of the nuclei with the subsequent growth of the nanostructure and morphology, and provide strategies to control and shape the mesostructure of Li metal to achieve high performance in rechargeable Li batteries.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Nanostructure evolution of Li deposit as a function of deposition time and current density.
Fig. 2: MD simulation of the nucleation process of Li metal.
Fig. 3: Microstructure and morphology of Li deposits after 1 mA h cm−2 plating.
Fig. 4: Correlation between crystallinity of Li metal and performance (left) and strategies to achieve better performance (right).
Fig. 5: The influence of electrolyte on the nano- and microstructure of Li deposits and the resulting performance.
Fig. 6: Simulated results of Li deposition at three different rates.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.


  1. 1.

    Steiger, J., Kramer, D. & Mönig, R. Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium. J. Power Sources 261, 112–119 (2014).

    CAS  Article  Google Scholar 

  2. 2.

    Wood, K. N. et al. Dendrites and pits: untangling the complex behavior of lithium metal anodes through operando video microscopy. ACS Cent. Sci. 2, 790–801 (2016).

    CAS  Article  Google Scholar 

  3. 3.

    Cohen, Y. S., Cohen, Y. & Aurbach, D. Micromorphological studies of lithium electrodes in alkyl carbonate solutions using in situ atomic force microscopy. J. Phys. Chem. B 104, 12282–12291 (2000).

    CAS  Article  Google Scholar 

  4. 4.

    Mogi, R., Inaba, M., Iriyama, Y., Abe, T. & Ogumi, Z. In situ atomic force microscopy study on lithium deposition on nickel substrates at elevated temperatures. J. Electrochem. Soc. 149, A385–A390 (2002).

    CAS  Article  Google Scholar 

  5. 5.

    Orsini, F. et al. In situ scanning electron microscopy (SEM) observation of interfaces within plastic lithium batteries. J. Power Sources 76, 19–29 (1998).

    CAS  Article  Google Scholar 

  6. 6.

    Cheng, J.-H. et al. Visualization of lithium plating and stripping via in operando transmission X-ray microscopy. J. Phys. Chem. C 121, 7761–7766 (2017).

    Article  Google Scholar 

  7. 7.

    Kushima, A. et al. Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: root growth, dead lithium and lithium flotsams. Nano Energy 32, 271–279 (2017).

    CAS  Article  Google Scholar 

  8. 8.

    Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy. Science 358, 506–510 (2017).

    CAS  Article  Google Scholar 

  9. 9.

    Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).

    CAS  Article  Google Scholar 

  10. 10.

    Dubrovskii, V. in Nucleation Theory and Growth of Nanostructures 1–73 (Springer, 2014).

  11. 11.

    Scharifker, B. R. & Mostany, J. in Encyclopedia of Electrochemistry 512–539 (Wiley, 2007).

  12. 12.

    Ely, D. R., Jana, A. & García, R. E. Phase field kinetics of lithium electrodeposits. J. Power Sources 272, 581–594 (2014).

    CAS  Article  Google Scholar 

  13. 13.

    Ely, D. R. & García, R. E. Heterogeneous nucleation and growth of lithium electrodeposits on negative electrodes. J. Electrochem. Soc. 160, A662–A668 (2013).

    CAS  Article  Google Scholar 

  14. 14.

    Akolkar, R. Modeling dendrite growth during lithium electrodeposition at sub-ambient temperature. J. Power Sources 246, 84–89 (2014).

    CAS  Article  Google Scholar 

  15. 15.

    Akolkar, R. Mathematical model of the dendritic growth during lithium electrodeposition. J. Power Sources 232, 23–28 (2013).

    CAS  Article  Google Scholar 

  16. 16.

    Chazalviel, J. N. Electrochemical aspects of the generation of ramified metallic electrodeposits. Phys. Rev. A 42, 7355–7367 (1990).

    CAS  Article  Google Scholar 

  17. 17.

    Wang, X., Li, Y. & Meng, Y. S. Cryogenic electron microscopy for characterizing and diagnosing batteries. Joule 2, 2225–2234 (2018).

    CAS  Article  Google Scholar 

  18. 18.

    Wang, F. et al. Chemical distribution and bonding of lithium in intercalated graphite: identification with optimized electron energy loss spectroscopy. ACS Nano 5, 1190–1197 (2011).

    CAS  Article  Google Scholar 

  19. 19.

    Loh, N. D. et al. Multistep nucleation of nanocrystals in aqueous solution. Nat. Chem. 9, 77–82 (2017).

    CAS  Article  Google Scholar 

  20. 20.

    Yang, J. et al. Amorphous-phase-mediated crystallization of Ni nanocrystals revealed by high-resolution liquid-phase electron microscopy. J. Am. Chem. Soc. 141, 763–768 (2019).

    CAS  Article  Google Scholar 

  21. 21.

    Liao, H.-G., Cui, L., Whitelam, S. & Zheng, H. Real-time imaging of Pt3Fe nanorod growth in solution. Science 336, 1011–1014 (2012).

    CAS  Article  Google Scholar 

  22. 22.

    Wittig, J. E., Bentley, J. & Allard, L. F. In situ investigation of ordering phase transformations in FePt magnetic nanoparticles. Ultramicroscopy 176, 218–232 (2017).

    CAS  Article  Google Scholar 

  23. 23.

    Chi, M. et al. Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing. Nat. Commun. 6, 8925 (2015).

    CAS  Article  Google Scholar 

  24. 24.

    van Duin, A. C. T., Dasgupta, S., Lorant, F. & Goddard, W. A. ReaxFF: a reactive force field for hydrocarbons. J. Phys. Chem. A 105, 9396–9409 (2001).

    Article  Google Scholar 

  25. 25.

    Plimpton, S., Crozier, P. & Thompson, A. LAMMPS-large-scale atomic/molecular massively parallel simulator. Sandia Natl Laboratories 18, 43 (2007).

    Google Scholar 

  26. 26.

    Majure, D. L. et al. Large-scale atomic/molecular massively parallel simulator (LAMMPS) simulations of the effects of chirality and diameter on the pullout force in a carbon nanotube bundle. In 2008 DoD HPCMP Users Group Conference 201–207 (IEEE, 2008).

  27. 27.

    Stukowski, A. Visualization and analysis of atomistic simulation data with OVITO–the open visualization tool. Model. Simul. Mater. Sci. Eng. 18, 015012 (2009).

    Article  Google Scholar 

  28. 28.

    Onofrio, N. & Strachan, A. Voltage equilibration for reactive atomistic simulations of electrochemical processes. J. Chem. Phys. 143, 054109 (2015).

    Article  Google Scholar 

  29. 29.

    Jensen, B. D., Wise, K. E. & Odegard, G. M. The effect of time step, thermostat, and strain rate on ReaxFF simulations of mechanical failure in diamond, graphene, and carbon nanotube. J. Comput. Chem. 36, 1587–1596 (2015).

    CAS  Article  Google Scholar 

  30. 30.

    Cui, Z., Gao, F., Cui, Z. & Qu, J. Developing a second nearest-neighbor modified embedded atom method interatomic potential for lithium. Model. Simul. Mater. Sci. Eng. 20, 015014 (2011).

    Article  Google Scholar 

  31. 31.

    Stukowski, A. Structure identification methods for atomistic simulations of crystalline materials. Model. Simul. Mater. Sci. Eng. 20, 045021 (2012).

    Article  Google Scholar 

  32. 32.

    Baldan, A. Review progress in Ostwald ripening theories and their applications to nickel-base superalloys part I: Ostwald ripening theories. J. Mater. Sci. 37, 2171–2202 (2002).

    CAS  Article  Google Scholar 

  33. 33.

    Nanev, C. N. in Handbook of Crystal Growth 2nd edn, 315–358 (Elsevier, 2015).

  34. 34.

    Karthika, S., Radhakrishnan, T. K. & Kalaichelvi, P. A review of classical and nonclassical nucleation theories. Cryst. Growth Des. 16, 6663–6681 (2016).

    CAS  Article  Google Scholar 

  35. 35.

    Greer, A. L. Metallic glasses. Science 267, 1947–1953 (1995).

    CAS  Article  Google Scholar 

  36. 36.

    Jafary-Zadeh, M. et al. A critical review on metallic glasses as structural materials for cardiovascular stent applications. J. Funct. Biomater. 9, 19 (2018).

    Article  Google Scholar 

  37. 37.

    Chen, M. A brief overview of bulk metallic glasses. NPG Asia Mater. 3, 82–90 (2011).

    Google Scholar 

  38. 38.

    Khan, M. M. et al. Recent advancements in bulk metallic glasses and their applications: a review. Crit. Rev. Solid State Mater. Sci. 43, 233–268 (2018).

    CAS  Article  Google Scholar 

Download references


We thank the UC Irvine Materials Research Institute (IMRI) for the use of the Cryo-Electron Microscopy Facility and Kratos XPS, funded in part by the National Science Foundation Major Research Instrumentation Program under grant no. CHE-1338173. We thank X. Pan, T. Aoki, L. Xing and J.-G. Zheng for their assistance with the microscopy. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. The SEM was performed in part at the San Diego Nanotechnology Infrastructure (SDNI), a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (grant ECCS-1542148). We also thank A. van Duin of the Pennsylvania State University for providing the ReaxFF parameters used in this work. We thank W. Xu and M. Olguin for discussing the results. This work is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy in the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium). Idaho National Laboratory (INL) is operated by Battelle Energy Alliance under contract no. DE-DE-AC07-05ID14517 for the US Department of Energy.

Author information




X.W., Y.S.M. and B.L. conceived the idea. X.W. designed the experiments and conducted the cryo-TEM. Y.L., B.L., M.Z. and A.B. helped with cell making, electrochemical performance evaluation, EELS and SEM. X.W., Y.L. and Y.S.M. analysed and discussed the experimental data. X.W. and Y.L. made the schematic images. G.P., E.D. and B.L. developed the concept of the r-MD approach. G.P. conducted the simulation work. B.L. provided the major interpretation and discussion of the r-MD results in the paper. X.R. and J.Z. provided the advanced electrolyte and the anode-free electrochemical performance. P.L., J.X., J.L. and E.D. participated in discussing the results and commenting on the manuscript. The manuscript was mainly written and revised by X.W., B.L., G.P. and Y.S.M. All authors approved the final version of the manuscript.

Corresponding authors

Correspondence to Ying Shirley Meng or Boryann Liaw.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Co-first authors: Xuefeng Wang, Gorakh Pawar.

Extended data

Extended Data Fig. 1 Influence of local mass transport, energy transfer and current density (as represented by packing density) on the nucleation and phase transition of Li metal deposits by using ensembles of 600 Li atoms as the basis for the simulation.

The packing density in a-d is 0.0534, 0.13, 0.27 and 0.47 g cm−3 respectively. The crystal structure (that is the bcc lattice) is represented in blue, whereas the amorphous fractions or phases in white or grey.

Extended Data Fig. 2

Cryo-TEM images (a-d) and their FFT patterns (e-h) of Li deposits at 0.5 mA cm-2 for 2h. Besides (110) plane of Li metal, lattice fringes or FFT spots with lattice spacing of ~0.174 and ~0.142 nm was also observed, which belongs to the (200) and (211) planes of Li metal, respectively. Specially in d and h, both (200) and (110) planes of Li metal are present, which helps to determine the zone axis of [001] and confirm the phase of Li metal.

Extended Data Fig. 3

Cryogenic STEM image (a), EELS Mapping (b) and spectra (c) of EDLi obtained at 0.5 mA cm-2 for 2h. The EELS mapping (b) is based on the intensity EELS spectra ranging from 53.5 eV to 58.5 eV (highlighted by the blue square in c), which contains the characteristic metallic/elemental Li K-edge threshold at about 55 eV. c presents the EELS spectra taken from Area 1 and Area 2 (labeled in b) representing the feature of highly crystalline Li and glassy Li respectively. Due to the presumed same SEI on the surface of Area 1 and Area 2, they show similar extended fine structure of Li K-edge after 60 eV. Both of them have the obvious characteristic metallic/elemental Li K-edge threshold at about 55 eV while the highly crystalline Li Area 1 shows a peak with slightly higher intensity than the glassy Li Area 2. This is reasonable due to the different degree of order/disorder structure in these two areas. It is worth to noting that it is difficult to obtain the higher-resolution STEM mapping due to the radiation damage caused by the high-energy beam used for STEM scanning even at cryogenic temperature. Source data

Extended Data Fig. 4 Nanostructure evolution of Na, K, Mg and Zn deposits as a function of current density.

TEM images (a-d and i-l) and the corresponding FFT patterns (e-h and m-p) of Na at 0.1 mA cm−2 (a and e) and 0.5 mA cm−2 (i and m), K at 0.1 mA cm−2 (b and f) and 0.5 mA cm−2 (j and n), Mg at 0.05 mA cm−2 (c and g) and 0.1 mA cm−2 (k and o) and Zn at 0.1 mA cm−2 (d and h) and 0.5 mA cm−2 (l and p). The crystalline portion of the Na, K, Mg, and Zn deposits are labeled by the white dash lines.

Supplementary information

Supplementary Information

Supplementary Figs. 1–21, discussion and Tables 1–2.

Supplementary Video 1

The heating stage during the simulated annealing approach. The kinetics of the Li nucleation are intriguing. Several nucleation sites rapidly formed and continued to evolve, showing substantial variability in the nucleation kinetics.

Supplementary Video 2

The quenching stage during the simulated annealing approach. The coarsening and condensation of intermediate Li nucleation sites (nuclei) resulted in crystalline clusters with sizes in the range of 2–5 nm. This crystalline cluster size range is critical in determining the material’s reactivity in practical applications.

Supplementary Video 3

The equilibration stage during the simulated annealing approach. The cluster that evolved through maturation either remained in an amorphous state at lower current densities or transformed into a ‘crystalline’ state at higher current densities.

Supplementary Video 4

The condensation process at a relatively lower current density (for example, an ensemble with 500 Li atoms). The Li aggregate remained amorphous even after 5.3 ns in simulation. Irrespective of the timescale, the nanostructure is the key that could substantially impact the underlying material’s properties and have profound implications in a variety of applications such as in electrodeposition, catalysis, semiconductor fabrication and so on.

Supplementary Video 5

The condensation process at a relatively moderate current density (for example, an ensemble with 700 Li atoms). The condensed Li aggregate remained in an amorphous state with a long incubation time (>2 ns) and eventually transformed into a nucleus structure.

Supplementary Video 6

The condensation process at a relatively higher current density (for example, an ensemble with 900 Li atoms). The initial amorphous Li cluster rapidly transformed into a crystalline structure with a substantially short incubation time (<0.7 ns). Accessing such information at the nanosecond and/or picosecond timescales could be challenging with the experimental methods.

Source data

Source Data Fig. 2

Numerical data.

Source Data Fig. 5

Numerical data.

Source Data Extended Data Fig. 3

Numerical data.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wang, X., Pawar, G., Li, Y. et al. Glassy Li metal anode for high-performance rechargeable Li batteries. Nat. Mater. (2020).

Download citation