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Breaking the molecular symmetricity of sulfonimide anions for high-performance lithium metal batteries under extreme cycling conditions

Nature Energy volume 10, pages 191–204 (2025)Cite this article

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Abstract

Lithium metal batteries operating under extreme conditions are limited by the sluggish desolvation process and poor stability of the electrode–electrolyte interphase. However, rational interphase design is hindered by the ill-defined understanding of interphasial chemistry at the molecular level. Here we design and synthesize a series of sulfoximide salts, lithium bis(trifluoromethanesulfinyl)imide (LiBSTFSI) and lithium (trifluoromethanesulfinyl)(trifluoromethanesulfonyl)imide (LiSTFSI), that possess distinctive oxidizability. Their molecular structure and interphasial chemistry were correlated. An anionic electro-polymerization was induced by the asymmetric LiSTFSI to establish a bilayer catholde–electrolyte interphase (CEI) with LiF dominated inner covered by negative-charged inorganic polymers. LiSTFSI-derived CEI enables superior mechanical stability and accelerated Li+ desolvation that contribute to the stable cycling and superior energy and power densities under ultra-high rate and ultra-low temperature conditions. Industrial pouch cells of 474 Wh kg−1 achieved extreme power density of 5,080 W kg−1 at 30 °C and exceptional low-temperature energy and power densities at −20 °C (382 Wh kg−1, 3,590 W kg−1) and −40 °C (321 Wh kg−1, 1,517 W kg−1).

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Fig. 1: Design scheme and principle of LiBSTFSI and LiSTFSI.
Fig. 2: Physicochemical and electrochemical properties of the TFSI−, STFSI− and BSTFSI− anions.
Fig. 3: Electrochemical performance and characterizations of ether-based electrolyte with different lithium salt additives.
Fig. 4: Structural and component characterizations of cycled NMC811 cathodes and CEI.
Fig. 5: Experimental and theoretical studies on the interphasial chemistry.
Fig. 6: Formation mechanism and structural evolution of LiSTFSI-derived CEI.
Fig. 7: Mechanical properties of inorganic polymers in LiSTFSI-derived CEI.
Fig. 8: Li/NMC811 cell performance under extreme conditions enabled by LiSTFSI-derived CEI.

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Data availability

The datasets analysed and generated during the current study are included in the main text and its Supplementary Information.

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Acknowledgements

This work was supported by the National Science Foundation of China (grant number 22071133, K.L.), the National Key Research and Development Program (grant number 2023YFB2503700, K.L.), the National Key Research and Development Program (grant number 2023YFC3008804, K.L.), the Beijing Natural Science Foundation (grant number Z220020, K.L.). We thank H. Wang for the support on characterization instruments, J. Yue from Bruker (Beijing) Scientific Technology Co., Ltd., for the assistance of AFM-PF-QNM measurements and C. Guo from Analysis Center, Tsinghua University, for analysing TOF-SIMS data.

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  1. These authors contributed equally: Yang Lu, Qingbin Cao, Weili Zhang.

Authors and Affiliations

  1. Department of Chemical Engineering, Tsinghua University, Beijing, China

    Yang Lu, Qingbin Cao, Weili Zhang, Yu Ou, Shuaishuai Yan, Hao Liu, Xuan Song, Haiyu Zhou, Wenhui Hou, Pan Zhou & Kai Liu

  2. Hefei Institute for Public Safety Research, Tsinghua University, Hefei, China

    Weili Zhang, Tianyou Zeng, Hao Liu & Qingqing Feng

  3. Agilent Technologies (China), Beijing, China

    Nan Hu

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

    Yong Li

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Contributions

Y. Lu and K.L. conceived the idea and designed the experiments. Y. Lu performed the material characterizations and electrochemical measurements with assistance from Q.C., W.Z. and T.Z. Y.O., S.Y., H.L., X.S., H.Z., W.H., P.Z. and Q.F. helped with discussion. N.H. provided assistance with LC-QTOF-MS experiments. Y. Li provided some testing materials. Y. Lu and K.L. analysed the data and prepared the paper with contributions from all authors.

Corresponding author

Correspondence to Kai Liu.

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Lu, Y., Cao, Q., Zhang, W. et al. Breaking the molecular symmetricity of sulfonimide anions for high-performance lithium metal batteries under extreme cycling conditions. Nat Energy 10, 191–204 (2025). https://doi.org/10.1038/s41560-024-01679-4

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