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Enhancing lithium-metal battery longevity through minimized coordinating diluent

Nature Energy (2024)Cite this article

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Abstract

Extending the lifespan of lithium (Li) batteries involves managing reactions at the Li anode and stabilizing the solid–electrolyte interphase (SEI) through strategic regulation of the electrolyte composition. Here we synthesized a fluorinated cyclic ether with minimized Li-ion coordination capability and enhanced electrochemical stability. We demonstrated its crucial role in manipulating the SEI formation process by differentiating the contribution of dual anions to the SEI layer. Consequently, a bilayer SEI is formed, featuring a Li2O-rich inner layer and a LiF-rich outer layer, enabling improved stability and reversibility of Li-metal anodes. The developed electrolyte shows remarkable improvement in calendar life and cycling stability of Li (50 µm)||NMC811 (4 mAh cm−2) cells, maintaining 80% capacity after 568 and 218 cycles at room temperature and 60 °C, respectively. Furthermore, our 410 Wh kg−1 prototype pouch cells demonstrate 80% capacity retention for 470 cycles.

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Fig. 1: Fluorinated cyclic ether with minimized Li-ion coordination and the promoted stable SEI.
Fig. 2: Studies on the coordination interaction between Li ion and diluents BTFE, TTE and HFTHP by 19F and 17O NMR techniques.
Fig. 3: SEM studies on Li deposition morphologies and XPS depth profiles on the formed SEIs in different electrolytes.
Fig. 4: Nanostructures of the formed SEI and the differentiated coordination between Li ion with anions DFOB− and BF4− in D-HFTHP.
Fig. 5: Evaluation of self-discharge of the Li||NMC811 full cells in electrolytes and cycling performance at 60 °C.
Fig. 6: Cycling performance of Li||NMC811 cells and the evolution of electrolytes upon cycling.

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The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the Advanced Battery Materials Research Program (Battery500 Consortium) and Battelle-Pacific Northwest National Laboratory Subcontract Award 614551. We gratefully acknowledge the computing resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory.

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Authors and Affiliations

  1. Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA

    Guo-Xing Li, Rong Kou, Heng Jiang, Meng Liao & Donghai Wang

  2. Department of Chemical Engineering, University of Illinois Chicago, Chicago, IL, USA

    Volodymyr Koverga, Musawenkosi Ncube, Hanzeng Guo, Jun Chen, Naveen Dandu & Anh T. Ngo

  3. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Volodymyr Koverga, Musawenkosi Ncube, Hanzeng Guo, Jun Chen, Naveen Dandu & Anh T. Ngo

  4. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

    Au Nguyen

  5. Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    Ke Wang

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Contributions

G.-X.L. and D.W. conceived and designed the idea. G.-X.L., R.K. and H.J. conducted the electrochemical tests and 1H, 13C, 17O and 19F NMR characterizations. A.N. and M.L. conducted and analysed the XPS depth-profiling characterization. V.K., M.N., H.G., J.C. and N.D. performed molecular dynamics and DFT simulations. A.T.N. supervised the molecular modelling. K.W. conducted the cryo-TEM experiments. G.-X.L. and D.W. wrote and revised the paper.

Corresponding authors

Correspondence to Anh T. Ngo or Donghai Wang.

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

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Supplementary Figs. 1–52, Tables 1–3 and Discussion.

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Li, GX., Koverga, V., Nguyen, A. et al. Enhancing lithium-metal battery longevity through minimized coordinating diluent. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01519-5

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