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Electrode potential influences the reversibility of lithium-metal anodes

Abstract

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%).

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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.

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Acknowledgements

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.

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Contributions

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.

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The authors declare no competing interests.

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

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Supplementary Information

Supplementary Note 1, Table 1 and Figs. 1–11.

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Ko, S., Obukata, T., Shimada, T. et al. Electrode potential influences the reversibility of lithium-metal anodes. Nat Energy 7, 1217–1224 (2022). https://doi.org/10.1038/s41560-022-01144-0

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