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Unified affinity paradigm for the rational design of high-efficiency lithium metal electrolytes

Nature Energy volume 10, pages 1155–1165 (2025)Cite this article

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Abstract

Electrolyte engineering breakthroughs are crucial to support extremely high-energy battery chemistries. However, the complex interplay between battery performance and electrolyte structure remains poorly understood and difficult to predict. Here we introduce the concept of ‘normalized cation/anion–solvent affinity’, which describes the critical interactions between solvents and both cations and anions. This innovative approach allows for the simultaneous and quantitative prediction of electrolyte microstructures, transport characteristics, redox behaviours and interphase characteristics. Leveraging this framework, we screened approximately 150 solvent candidates and identified electrolyte formulations that significantly improve Li metal plating/stripping Coulombic efficiency ( >99.5%). Among these, four electrolytes achieved Coulombic efficiency greater than 99.8%, while supporting the durability of aggressive high-voltage cathodes. These formulations enabled the realization of highly reversible Li metal batteries (LMBs) with a record-breaking high energy density of 600 Wh kg−1 and over 100 cycles, advancing LMBs towards practical applications. The unified affinity paradigm offers valuable insights for designing next-generation electrolytes for high-energy LMBs and other alkali-metal-ion batteries.

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Fig. 1: Solvation structure formation mechanism and scaling relationship with the ion–solvent interaction energetics.
Fig. 2: Ion–solvent affinities for representative solvents and their use for electrolyte design.
Fig. 3: Transport behaviour of electrolyte and relationship with the ion–solvent affinities.
Fig. 4: Electrochemical redox mechanism of solvent and scaling relationship between redox potential and the charge transfer.
Fig. 5: Electrochemical performances of Li metal batteries in different electrolytes.

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All data supporting the conclusions of this study are provided within the main article and its Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2024YFB3814300), Natural Science Foundation of Zhejiang Province (LR23B030002), National Natural Science Foundation of China (22409176 and U21A2081), Fundamental Research Funds for the Central Universities (226-2024-00075) and ‘Hundred Talents Program’ of Zhejiang University.

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Author notes

  1. These authors contributed equally: Ruhong Li, Haikuo Zhang.

Authors and Affiliations

  1. State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, China

    Ruhong Li, Haikuo Zhang, Shuoqing Zhang, Junbo Zhang, Long Chen, Xuezhang Xiao, Lixin Chen & Xiulin Fan

  2. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, China

    Ruhong Li

  3. State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai, China

    Yong Li, Rui Guo & Haijuan Pei

  4. Science and Technology on Power Sources Laboratory, Tianjin Institute of Power Sources, Tianjin, China

    Ming Yang

  5. i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO), Chinese Academy of Sciences, Suzhou, China

    Yanbin Shen

  6. China-UK Low Carbon College, Shanghai Jiao Tong University, Shanghai, China

    Tao Deng

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  1. Ruhong Li
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Contributions

R.L. and X.F. conceived the idea and designed the experiments. R.L. and H.Z. provided the theoretical simulations. R.L., H.Z., S.Z. and J.Z. conducted the electrochemical experiments and characterizations. Long Chen, X.X., Lixin Chen, Y.S. and T.D. participated in the scientific discussion and data analysis. Y.L., R.G., M.Y. and H.P. carried out the electrochemical test of pouch cells. R.L. and X.F. prepared the manuscript with the input of all the co-authors. All authors endorsed the final version of the manuscript.

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Correspondence to Xiulin Fan.

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Li, R., Zhang, H., Zhang, S. et al. Unified affinity paradigm for the rational design of high-efficiency lithium metal electrolytes. Nat Energy 10, 1155–1165 (2025). https://doi.org/10.1038/s41560-025-01842-5

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