Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis


Anode-free lithium metal cells store 60% more energy per volume than conventional lithium-ion cells. Such high energy density can increase the range of electric vehicles by approximately 280 km or even enable electrified urban aviation. However, these cells tend to experience rapid capacity loss and short cycle life. Furthermore, safety issues concerning metallic lithium often remain unaddressed in the literature. Recently, we demonstrated long-lifetime anode-free cells using a dual-salt carbonate electrolyte. Here we characterize the degradation of anode-free cells with this lean (2.6 g Ah−1) liquid electrolyte. We observe deterioration of the pristine lithium morphology using scanning electron microscopy and X-ray tomography, and diagnose the cause as electrolyte degradation and depletion using nuclear magnetic resonance spectroscopy and ultrasonic transmission mapping. For the safety characterization tests, we measure the cell temperature during nail penetration. Finally, we use the insights gained in this work to develop an optimized electrolyte, extending the lifetime of anode-free cells to 200 cycles.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it


Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Comparison of anode-free and lithium-ion cells.
Fig. 2: Energy retention and lithium morphology.
Fig. 3: Electrochemical and electrolyte analysis.
Fig. 4: Evolution of lithium morphology.
Fig. 5: The impact of increasing porosity.
Fig. 6: Safety characterization.
Fig. 7: High-concentration dual-salt electrolyte.

Data availability

All relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.


  1. Kasliwal, A. et al. Role of flying cars in sustainable mobility. Nat. Commun. 10, 1555 (2019).

    Google Scholar 

  2. Holden, J. & Goel, N. Fast-forwarding to a Future of On-demand Urban Air Transportation (Uber Elevate, 2016);

  3. Blomgren, G. E. The development and future of lithium ion batteries. J. Electrochem. Soc. 164, A5019–A5025 (2017).

    Google Scholar 

  4. Neudecker, B. J., Dudney, N. J. & Bates, J. B. ‘Lithium-free’ thin-film battery with in situ plated Li anode. J. Electrochem. Soc. 147, 517 (2000).

    Google Scholar 

  5. Qian, J. et al. Anode-free rechargeable lithium metal batteries. Adv. Funct. Mater. 26, 7094–7102 (2016).

    Google Scholar 

  6. Albertus, P., Babinec, S., Litzelman, S. & Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2018).

    Google Scholar 

  7. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    Google Scholar 

  8. Schmuch, R., Wagner, R., Hörpel, G., Placke, T. & Winter, M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat. Energy 3, 267–278 (2018).

    Google Scholar 

  9. Betz, J. et al. Theoretical versus practical energy: a plea for more transparency in the energy calculation of different rechargeable battery systems. Adv. Energy Mater. 9, 1803170 (2018).

    Google Scholar 

  10. Abrha, L. H. et al. Li7La2.75Ca0.25Zr1.75Nb0.25O12@LiClO4 composite film derived solid electrolyte interphase for anode-free lithium metal battery. Electrochim. Acta 325, 134825 (2019).

    Google Scholar 

  11. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiaded graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405–416 (2002).

    Google Scholar 

  12. Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

    Google Scholar 

  13. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).

    Google Scholar 

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

    Google Scholar 

  15. 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).

    Google Scholar 

  16. López, C. M., Vaughey, J. T. & Dees, D. W. Morphological transitions on lithium metal anodes. J. Electrochem. Soc. 156, A726 (2009).

    Google Scholar 

  17. Rodriguez, R. et al. Separator-free and concentrated LiNO3 electrolyte cells enable uniform lithium electrodeposition. J. Mater. Chem. A (2020).

  18. Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).

    Google Scholar 

  19. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1–7 (2018).

    Google Scholar 

  20. Wilkinson, D. P., Blom, H., Brandt, K. & Wainwright, D. Effects of physical constraints on Li cyclability. J. Power Sources 36, 517–527 (1991).

    Google Scholar 

  21. Louli, A. J. et al. Exploring the impact of mechanical pressure on the performance of anode-free lithium metal cells. J. Electrochem. Soc. 166, A1291–A1299 (2019).

    Google Scholar 

  22. Yin, X. et al. Insights into morphological evolution and cycling behaviour of lithium metal anode under mechanical pressure. Nano Energy 50, 659–664 (2018).

    Google Scholar 

  23. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).

    Google Scholar 

  24. Brandt, K. Historical development of secondary lithium batteries. Solid State Ion. 69, 173–183 (1994).

    Google Scholar 

  25. Zhang, H. et al. Ionic liquid electrolyte with highly concentrated LiTFSI for lithium metal batteries. Electrochim. Acta 285, 78–85 (2018).

    Google Scholar 

  26. Guo, Q. et al. Flame retardant and stable Li1.5Al0.5Ge1.5(PO4)3-supported ionic liquid gel polymer electrolytes for high safety rechargeable solid-state lithium metal batteries. J. Phys. Chem. C 122, 10334–10342 (2018).

    Google Scholar 

  27. von Saken, U., Nodwell, E., Sundher, A. & Dahn, J. R. Comparative thermal stability of carbon intercalation anodes and lithium metal anodes for rechargeable lithium batteries. J. Power Sources 54, 240–245 (1995).

    Google Scholar 

  28. Zhou, Q. et al. A temperature-responsive electrolyte endowing superior safety characteristic of lithium metal batteries. Adv. Energy Mater. 10, 1–8 (2020).

    Google Scholar 

  29. Weber, R. et al. Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019).

    Google Scholar 

  30. Smith, A. J., Burns, J. C., Xiong, D. & Dahn, J. R. Interpreting high precision coulometry results on Li-ion cells. J. Electrochem. Soc. 158, A1136–A1142 (2011).

    Google Scholar 

  31. Nelson, K. J. et al. Studies of the effect of high voltage on the impedance and cycling performance of Li[Ni0.4Mn0.4Co0.2]O2/graphite lithium-ion pouch cells. J. Electrochem. Soc. 162, A1046–A1054 (2015).

    Google Scholar 

  32. Nelson, K. Studies of the Effects of High Voltage on the Performance and Impedance of Lithium-ion Batteries. PhD thesis, Dalhousie Univ. (2017).

  33. Zhu, Y., Li, Y., Bettge, M. & Abraham, D. P. Positive electrode passivation by LiDFOB electrolyte additive in high-capacity lithium-ion cells. J. Electrochem. Soc. 159, A2109–A2117 (2012).

    Google Scholar 

  34. Cha, J., Han, J. G., Hwang, J., Cho, J. & Choi, N. S. Mechanisms for electrochemical performance enhancement by the salt-type electrolyte additive, lithium difluoro(oxalato)borate, in high-voltage lithium-ion batteries. J. Power Sources 357, 97–106 (2017).

    Google Scholar 

  35. Chen, X. et al. Reduction mechanism of fluoroethylene carbonate for stable solid-electrolyte interphase film on silicon anode. ChemSusChem 7, 549–554 (2014).

    Google Scholar 

  36. Streich, D. et al. Online electrochemical mass spectrometry of high energy lithium nickel cobalt manganese oxide/graphite half- and full-cells with ethylene carbonate and fluoroethylene carbonate based electrolytes. J. Electrochem. Soc. 163, A964–A970 (2016).

    Google Scholar 

  37. Nakai, H., Kubota, T., Kita, A. & Kawashima, A. Investigation of the solid electrolyte interphase formed by fluoroethylene carbonate on Si electrodes. J. Electrochem. Soc. 158, A798 (2011).

    Google Scholar 

  38. Schroder, K. et al. The effect of fluoroethylene carbonate as an additive on the solid electrolyte interphase on silicon lithium-ion electrodes. Chem. Mater. 27, 5531–5542 (2015).

    Google Scholar 

  39. Jung, R. et al. Consumption of fluoroethylene carbonate (FEC) on Si-C composite electrodes for Li-ion batteries. J. Electrochem. Soc. 163, A1705–A1716 (2016).

    Google Scholar 

  40. Petibon, R. et al. Studies of the capacity fade mechanisms of LiCoO2/Si-alloy:graphite cells. J. Electrochem. Soc. 163, A1146–A1156 (2016).

    Google Scholar 

  41. Xu, C. et al. Improved performance of the silicon anode for Li-ion batteries: understanding the surface modification mechanism of fluoroethylene carbonate as an effective electrolyte additive. Chem. Mater. 27, 2591–2599 (2015).

    Google Scholar 

  42. Parimalam, B. S. & Lucht, B. L. Reduction reactions of electrolyte salts for lithium ion batteries: LiPF6, LiBF4, LiDFOB, LiBOB, and LiTFSI. J. Electrochem. Soc. 165, A251–A255 (2018).

    Google Scholar 

  43. Allen, J. L., Han, S. D., Boyle, P. D. & Henderson, W. A. Crystal structure and physical properties of lithium difluoro(oxalato) borate (LiDFOB or LiBF2Ox). J. Power Sources 196, 9737–9742 (2011).

    Google Scholar 

  44. Jurng, S., Brown, Z. L., Kim, J. & Lucht, B. L. Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes. Energy Environ. Sci. (2018).

  45. Bommier, C. et al. In operando acoustic detection of lithium metal plating in commercial LiCoO2/Graphite pouch cells. Cell Rep. Phys. Sci. (2020).

  46. Deng, Z. et al. Observation of the electrolyte wetting and ‘unwetting’ in Li-ion pouch cells via ultrasonic scanning technology. Joule (2020).

  47. Hatchard, T. D., Trussler, S. & Dahn, J. R. Building a ‘smart nail’ for penetration tests on Li-ion cells. J. Power Sources 247, 821–823 (2014).

    Google Scholar 

  48. Genovese, M. et al. Hot formation for improved low temperature cycling of anode-free lithium metal batteries. J. Electrochem. Soc. 166, A3342–A3347 (2019).

    Google Scholar 

  49. Li, J. et al. Comparison of single crystal and polycrystalline LiNi0.5Mn0.3Co0.2O2 positive electrode materials for high voltage Li-ion cells. J. Electrochem. Soc. 164, A1534–A1544 (2017).

    Google Scholar 

Download references


This research was financially supported by Tesla Canada and NSERC under the Industrial Research Chairs Program. A.J.L. and A.E. thank NSERC, the Killam Foundation and the Nova Scotia Graduate Scholarship programmes for financial support. M.G. thanks the NSERC PDF Program. We acknowledge J. Li (formerly of BASF) and D. J. Xiong (formerly of Capchem) for providing the chemicals used in the electrolytes. We also acknowledge P. Scallion for SEM support, as well as S. Trussler for expert fabrication of the parts used in this work.

Author information

Authors and Affiliations



A.J.L., M.G., R.W. and J.R.D. conceived the idea. A.J.L. performed the electrochemical measurements and the SEM analysis with the assistance of M.C. and J.d.G. A.E. and R.W. performed and analysed the NMR experiments with the assistance of M.C. and J.d.G. X-ray tomography was performed by R.T.W., J.L. and T.R. A.J.L. performed the safety characterization with the assistance of J.d.G. Z.D. performed the ultrasonic transmission mapping measurements. R.P., S.J.H.C. and S.H. contributed to useful discussions. A.J.L., A.E. and J.R.D. prepared the manuscript with input from all other co-authors.

Corresponding author

Correspondence to J. R. Dahn.

Ethics declarations

Competing interests

R.W., R.P., S.H. and S.J.H.C. are employed by Tesla Canada R&D. R.T.W., J.L. and T.R. are employed by Carl Zeiss Microscopy.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Table 1, Figs. 1–16 and discussion.

Supplementary Video 1

Submerge and observe qualitative reactivity test pictured in Fig. 6. Charged negative electrode (graphite and plated lithium) samples retrieved from cycled pouch cells at the top of charge are submerged into water to observe their reactivity. The electrolyte chemistries used in the pouch cells from which these samples were retrieved are indicated in the video titles before each submersion.

Supplementary Video 2

Nail test videos pictured in Fig. 6. Anode-free pouch cells at the top of charge after being cycled 50 times were penetrated with nail. The electrolyte chemistries used in each pouch cell nailed are indicated in the video titles before each experiment.

Supplementary Data

Source data for Supplementary Figs. 1 and 2.

Source data

Source Data Fig. 2

Source data Fig. 2.

Source Data Fig. 3

Source data Fig. 3.

Source Data Fig. 6

Source data Fig. 6.

Source Data Fig. 7

Source data Fig. 7.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Louli, A.J., Eldesoky, A., Weber, R. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat Energy 5, 693–702 (2020).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing