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.

Electrode potential influences the reversibility of lithium-metal anodes


Lithium-metal batteries are a promising technology to address the emerging demand for high-energy-density storage systems. However, their cycling encounters a low Coulombic efficiency (CE) due to the unceasing electrolyte decomposition. Improving the stability of solid electrolyte interphase (SEI) suppresses the decomposition and increases CE. However, SEI morphology and chemistry alone cannot account for CE, and a full explanation is still lacking. Here we report that in diverse electrolytes, the large shift (>0.6 V) in the Li electrode potential and its association with the Li+ coordination structure influence the CE. Machine learning regression analysis and vibrational spectroscopy revealed that the formation of ion pairs is essential for upshifting the Li electrode potential, that is, for weakening the reducing ability of Li, which would lead to a high CE with diminished electrolyte decomposition. Various electrolytes with enhanced ion-pairing solution structure are designed to enable a significantly improved CE (>99%).

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

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: Electrolyte design concept.
Fig. 2: CEs of Li plating/stripping depending on ELi.
Fig. 3: Reversible Li plating/stripping enabled by electrode potential upshift in a weakly coordinating solvent, DMM.
Fig. 4: Statistical and vibrational correlation between coordination states and ELi.

Data availability

All the relevant data are included in the paper and its Supplementary Information.


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

    Article  Google Scholar 

  2. Liu, B., Zhang, J.-G. & Xu, W. Advancing lithium metal batteries. Joule 2, 833–845 (2018).

    Article  Google Scholar 

  3. Zhang, X., Yang, Y. & Zhou, Z. Towards practical lithium-metal anodes. Chem. Soc. Rev. 49, 3040–3071 (2020).

    Article  Google Scholar 

  4. Zhang, Y. et al. Towards better Li metal anodes: challenges and strategies. Mater. Today 33, 56–74 (2020).

    Article  Google Scholar 

  5. Cheng, X.-B. et al. A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3, 1500213 (2016).

    Article  Google Scholar 

  6. Tikekar, M. D., Choudhury, S., Tu, Z. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).

    Article  Google Scholar 

  7. Aurbach, D., Ein‐Ely, Y. & Zaban, A. The surface chemistry of lithium electrodes in alkyl carbonate solutions. J. Electrochem. Soc. 141, L1–L3 (1994).

    Article  Google Scholar 

  8. Ue, M. & Uosaki, K. Recent progress in liquid electrolytes for lithium metal batteries. Curr. Opin. Electrochem. 17, 106–113 (2019).

    Article  Google Scholar 

  9. Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Article  Google Scholar 

  10. Suo, L., Hu, Y.-S., Li, H., Armand, M. & Chen, L. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).

    Article  Google Scholar 

  11. Gao, X., Chen, Y., Johnson, L. & Bruce, P. G. Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions. Nat. Mater. 15, 882–888 (2016).

    Article  Google Scholar 

  12. Jiao, S. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3, 739–746 (2018).

    Article  Google Scholar 

  13. Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).

    Article  Google Scholar 

  14. Chen, M. et al. Marrying ester group with lithium salt: cellulose-acetate-enabled LiF-enriched interface for stable lithium metal anodes. Adv. Funct. Mater. 31, 2102228 (2021).

    Article  Google Scholar 

  15. Ko, J. & Yoon, Y. S. Recent progress in LiF materials for safe lithium metal anode of rechargeable batteries: is LiF the key to commercializing Li metal batteries? Ceram. Int. 45, 30–49 (2019).

    Article  Google Scholar 

  16. Mozhzhukhina, N. & Calvo, E. J. Perspective—the correct assessment of standard potentials of reference electrodes in non-aqueous solution. J. Electrochem. Soc. 164, A2295–A2297 (2017).

    Article  Google Scholar 

  17. Kim, S. C. et al. Potentiometric measurement to probe solvation energy and its correlation to lithium battery cyclability. J. Am. Chem. Soc. 143, 10301–10308 (2021).

    Article  Google Scholar 

  18. Seh, Z. W., Sun, J., Sun, Y. & Cui, Y. A highly reversible room-temperature sodium metal anode. ACS Cent. Sci. 1, 449–455 (2015).

    Article  Google Scholar 

  19. Doi, K. et al. Reversible sodium metal electrodes: is fluorine an essential interphasial component? Angew. Chem. Int. Ed. 58, 8024–8028 (2019).

    Article  Google Scholar 

  20. Yamada, Y. et al. Hydrate-melt electrolytes for high-energy-density aqueous batteries. Nat. Energy 1, 16129 (2016).

    Article  Google Scholar 

  21. Ko, S. et al. Lithium-salt monohydrate melt: a stable electrolyte for aqueous lithium-ion batteries. Electrochem. Commun. 104, 106488 (2019).

    Article  Google Scholar 

  22. Gagne, R. R., Koval, C. A. & Lisensky, G. C. Ferrocene as an internal standard for electrochemical measurements. Inorg. Chem. 19, 2854–2855 (1980).

    Article  Google Scholar 

  23. Gritzner, G. & Kůta, J. Recommendations on reporting electrode potentials in nonaqueous solvents: IUPC commission on electrochemistry. Electrochim. Acta 29, 869–873 (1984).

    Article  Google Scholar 

  24. Yamada, Y. et al. General observation of lithium intercalation into graphite in ethylene-carbonate-free superconcentrated electrolytes. ACS Appl. Mater. Interfaces 6, 10892–10899 (2014).

    Article  Google Scholar 

  25. Han, S.-D., Borodin, O., Seo, D. M., Zhou, Z.-B. & Henderson, W. A. Electrolyte solvation and ionic association. J. Electrochem. Soc. 161, A2042–A2053 (2014).

    Article  Google Scholar 

  26. Zhang, C. et al. Chelate effects in glyme/lithium bis(trifluoromethanesulfonyl)amide solvate ionic liquids. I. Stability of solvate cations and correlation with electrolyte properties. J. Phys. Chem. B 118, 5144–5153 (2014).

    Article  Google Scholar 

  27. Wiberg, K. B. & Murcko, M. A. Rotational barriers. 4. Dimethoxymethane. The anomeric effect revisited. J. Am. Chem. Soc. 111, 4821–4828 (1989).

    Article  Google Scholar 

  28. Tvaroška, I. & Bleha, T. Lone pair interactions in dimethoxymethane and anomeric effect. Can. J. Chem. 57, 424–435 (1979).

    Article  Google Scholar 

  29. Zhang, Z. et al. Capturing the swelling of solid–electrolyte interphase in lithium metal batteries. Science 375, 66–70 (2022).

    Article  Google Scholar 

  30. Wang, J., Wolf, R. M., Caldwell, J. W., Kollman, P. A. & Case, D. A. Development and testing of a general amber force field. J. Comput. Chem. 25, 1157–1174 (2004).

    Article  Google Scholar 

  31. Nishihara, S. & Otani, M. Hybrid solvation models for bulk, interface, and membrane: reference interaction site methods coupled with density functional theory. Phys. Rev. B 96, 2–3 (2017).

    Article  Google Scholar 

  32. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

    Article  Google Scholar 

  33. Spiegelman, C. H., Bennett, J. F., Vannucci, M., McShane, M. J. & Coté, G. L. A transparent tool for seemingly difficult calibrations: the parallel calibration method. Anal. Chem. 72, 135–140 (2000).

    Article  Google Scholar 

  34. Marini, F., Roncaglioni, A. & Novič, M. Variable selection and interpretation in structure—affinity correlation modeling of estrogen receptor binders. J. Chem. Inf. Model. 45, 1507–1519 (2005).

    Article  Google Scholar 

  35. Jalem, R., Aoyama, T., Nakayama, M. & Nogami, M. Multivariate method-assisted ab initio study of olivine-type LiMXO4 (main group M2+–X5+ and M3+–X4+) compositions as potential solid electrolytes. Chem. Mater. 24, 1357–1364 (2012).

Download references


This work was supported by the Advanced Low Carbon Technology Research and Development Program (ALCA), Specially Promoted Research for Innovative Next Generation Batteries (SPRING) of the Japan Science and Technology Agency (JST) (JPMJAL1301) to Y.Y.; JSPS KAKENHI Specially Promoted Research (number 15H05701) to A.Y.; and the Ministry of Education, Culture, Sports, Science and Technology (MEXT) Program: Data Creation and Utilization Type Materials Research and Development Project (JPMXP1121467561) to A.Y.

Author information

Authors and Affiliations



Y.Y. and A.Y. conceived and directed the projects. T.O., S.K. and Y.Y. proposed the concepts of the electrolyte design and electrode potential control. A.Y., N.T. and M.N. proposed the strategy and direction of the machine learning approach. S.K. and T.O. performed the experiments and analysed the data. T.S., N.T. and M.N. performed the computational and machine learning analyses. S.K., N.T., M.N., Y.Y. and A.Y. wrote the manuscript.

Corresponding authors

Correspondence to Atsuo Yamada or Yuki Yamada.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Venkatasubramanian Viswanathan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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 Note 1, Table 1 and Figs. 1–11.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ko, S., Obukata, T., Shimada, T. et al. Electrode potential influences the reversibility of lithium-metal anodes. Nat Energy 7, 1217–1224 (2022).

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