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Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries

Nature Energy volume 5, pages 386–397 (2020)Cite this article

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Abstract

Lithium batteries with Si, Al or Bi microsized (>10 µm) particle anodes promise a high capacity, ease of production, low cost and low environmental impact, yet they suffer from fast degradation and a low Coulombic efficiency. Here we demonstrate that a rationally designed electrolyte (2.0 M LiPF6 in 1:1 v/v mixture of tetrahydrofuran and 2-methyltetrahydrofuran) enables 100 cycles of full cells that contain microsized Si, Al and Bi anodes with commercial LiFePO4 and LiNi0.8Co0.15Al0.05O2 cathodes. Alloy anodes with areal capacities of more than 2.5 mAh cm−2 achieved >300 cycles with a high initial Coulombic efficiency of >90% and average Coulombic efficiency of >99.9%. These improvements are facilitated by the formation of a high-modulus LiF–organic bilayer interphase, in which LiF possesses a high interfacial energy with the alloy anode to accommodate plastic deformation of the lithiated alloy during cycling. This work provides a simple yet practical solution to current battery technology without any binder modification or special fabrication methods.

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Fig. 1: Effect of the SEI and electrolyte properties on the alloy anode particles.
Fig. 2: Cycling performance of SiMP electrodes in half-cells.
Fig. 3: Electrochemical performance of AlMP electrodes in half-cells.
Fig. 4: SEI chemical composition.
Fig. 5: LiF distribution on Si.
Fig. 6: Morphology of Si anodes after cycling.
Fig. 7: Cycling of the SiMP, BiMP and AlMP//LFP full cells.

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

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Acknowledgements

This project was supported by the Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE) through Battery500 Consortium under contract no. DE-EE0008202. Cryo-EM work was performed at the Center for Functional Nanomaterials, which is a US DOE Office of Science User Facility at Brookhaven National Laboratory, under Contract no. DE-SC0012704. Modelling work at the Army Research Laboratory (ARL) by O.B. was supported by ARL Enterprise for Multiscale Modeling. The authors acknowledge helpful discussions with M. Schroeder (ARL) and T. Pollard (ARL).

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  1. These authors contributed equally: Ji Chen, Xiulin Fan, Qin Li.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland College Park, College Park, MA, USA

    Ji Chen, Xiulin Fan, Qin Li, Long Chen, Xiao Ji, Chongyin Yang & Chunsheng Wang

  2. Department of Chemistry, Rutgers, The State University of New Jersey, New Brunswick, NJ, USA

    Hongbin Yang & Eric Garfunkel

  3. Department of Chemistry, Rutgers, The State University of New Jersey, Newark, NJ, USA

    M. Reza Khoshi & Huixin He

  4. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA

    Yaobin Xu & Chongmin Wang

  5. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Sooyeon Hwang & Dong Su

  6. Battery Science Branch, Sensor and Electron Devices Directorate, US Army Combat Capabilities Development Command Army Research Laboratory, Adelphi, MA, USA

    Oleg Borodin

  7. Department of Chemistry and Biochemistry, University of Maryland College Park, College Park, MA, USA

    Chunsheng Wang

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Contributions

J.C., X.F. and Q.L. contributed equally to this work. J.C., X.F. and C.W. conceived the idea for the project. J.C., X.F. and Q.L. prepared the materials and performed the electrochemical experiments. O.B. and X.J. conducted the QC calculations and MD simulations. M.R.K. and H.H. conducted the electrochemical AFM measurements. S.H., D.S., Y.X. and C.W. performed the cryo-TEM measurements. H.Y. and E.G. obtained the LiF spatial distribution and EELS spectra. L.C. and C.Y. coated the electrodes. All the authors discussed the results, analysed the data and drafted the manuscript.

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Correspondence to Oleg Borodin or Chunsheng Wang.

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A US patent with the provisional application number 62/978637 has been filed.

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Supplementary Notes 1–12, Figs. 1–41 and refs. 1–11.

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Chen, J., Fan, X., Li, Q. et al. Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries. Nat Energy 5, 386–397 (2020). https://doi.org/10.1038/s41560-020-0601-1

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