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Designing an asymmetric ether-like lithium salt to enable fast-cycling high-energy lithium metal batteries

Nature Energy volume 8, pages 934–945 (2023)Cite this article

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Abstract

Conventional carbonate-based electrolytes with high corrosion towards Li metal result in massive dendrite growth and limited cycling life, particularly true for practical Li-metal batteries with high cathode loading (>3.5 mAh cm−2). Herein we design an asymmetric Li salt, lithium 1,1,1-trifluoro-N-[2-[2-(2-methoxyethoxy)ethoxy)]ethyl] methanesulfonamide (LiFEA) that possesses a pseudo-crown ether-like, folded molecular geometry. It enables carbonate electrolytes with a large apparent donor number and Li+ transference number and drives a self-cleaning mechanism for solid–electrolyte interphases, enhancing compatibility with Li-metal anodes even at high current densities. LiFEA-based carbonate electrolytes notably improved fast-cycling performances of Li | |NCM811 cells. Pouch cells of 310 Wh kg−1 achieved ~410 W kg−1 power density at the discharging current density of 6.59 mA cm−2. Under fast-cycling conditions (charging: 1.46 mA cm−2, discharging: 3.66 mA cm−2), pouch cells maintained 81% capacity after 100 cycles. Our work provides insights into the interplay between the molecular structure of Li salts, their physicochemical properties and electrochemical performances.

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Fig. 1: Design principle of LiFEA.
Fig. 2: Experimental and theoretical study on pseudo-crown ether-like folded structure of LiFEA.
Fig. 3: Physicochemical properties of LiFEA and LiFEA-based electrolytes.
Fig. 4: Electrochemical performance of Li | |NCM811 batteries.
Fig. 5: Performance of Li | |NCM811 pouch cells under stringent conditions.
Fig. 6: Dendrite-free Li-deposited morphologies and plating/stripping reversibility under high current densities.
Fig. 7: LiFEA self-cleaning concept and results of EC-QCM experiments for SEIs.
Fig. 8: Components of SEIs with different soaking electrolytes and cycling electrolytes.

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Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information file. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Nature Science Fund of China (grant number 22071133, K. L.), Beijing Natural Science Foundation (grant number Z220020, K.L.), Recruitment Program of Guangdong (grant number 2016ZT06C322, X.K.), China Postdoctoral Science Foundation (grant number 2021M701872, Y.X.) and TCL Science and Technology Innovation Fund (X.K.). We thank C. Guo and Z. Li from Analysis Center, Tsinghua University for analysing the TOF-SIMs data, Y. Li from State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power Sources for helpful discussion and C. Cui from Chemistry and Chemical Engineering, Hunan University for discussing electrochemical measurements. We thank J. Fang (Tsinghua University) and Biolin Scientific AB for QCM experiments and data analysis.

Author information

Authors and Affiliations

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

    Yingchun Xia, Pan Zhou, Weili Zhang, Shuaishuai Yan, Wen-hui Hou, Hang-Yu Zhou, Hao Dong, Xiaoxia Chen, Peican Wang, Ziang Xu, Lei Wan, Baoguo Wang & Kai Liu

  2. South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou, China

    Xian Kong

  3. Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou, China

    Xian Kong

  4. Center of Pharmaceutical Technology, School of Pharmaceutical Sciences, Tsinghua University, Beijing, China

    Jiekang Tian

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  1. Yingchun Xia
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Contributions

Y.X. and K.L. conceived the idea and designed the experiments. Y.X., P.Z., X.K., J.T., W.Z., S.Y., W.-h.H., H.-Y.Z., Z.X. and L.W. carried out the experiments and measurements. H.D., X.C., P.W. and B.W. helped with discussion. Y.X., X.K. and K.L. analysed the data and prepared the manuscript with contributions from all authors.

Corresponding author

Correspondence to Kai Liu.

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Competing interests

For K. Liu and Y. Xia, this work has been filed as a China invention patent, patent number CN113871718B. The other authors declare no competing interests.

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Nature Energy thanks Hee-Tak Kim, Yuki Yamada and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–57, Notes 1–7 and Tables 1–7.

Source data

Source Data Fig. 3

Donor number data.

Source Data Fig. 5

Cycling data for pouch cells.

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Xia, Y., Zhou, P., Kong, X. et al. Designing an asymmetric ether-like lithium salt to enable fast-cycling high-energy lithium metal batteries. Nat Energy 8, 934–945 (2023). https://doi.org/10.1038/s41560-023-01282-z

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