Research ArticleELECTROCHEMISTRY

An ultrastable lithium metal anode enabled by designed metal fluoride spansules

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Science Advances  06 Mar 2020:
Vol. 6, no. 10, eaaz3112
DOI: 10.1126/sciadv.aaz3112
  • Fig. 1 Schematic illustration of the expected growth behavior of Li when plating on bare Cu foil and microspansule-modified Cu foil.

    (A) Behavior of Li nucleation and dendrite growth during Li plating on bare Cu foil. (B) Upon Li plating on microspansule-modified Cu foil, the in situ formation of M layer derived from dissolved metal ions of microspansules can effectively guide dendrite-free Li deposition. Meanwhile, with the concurrent supply of fluoride ions, a steady and LiF-rich SEI is formed outside the plated Li, leading to a uniform distribution of Li+ ion flux and stable Li electroplating.

  • Fig. 2 Fabrication strategy and characterizations of the NMMF@C microcubes.

    (A) Synthetic scheme of the NMMF@C cubes, which includes two steps: I, coating resorcinol-formaldehyde resin on the as-prepared cubes; II, carbonization at high temperature. (B) XRD pattern of the NMMF@C cubes together with two standard patterns. a.u., arbitrary units. (C) FESEM image of the NMMF cubes. (D) FESEM image of NMMF@C cubes. (E) TEM images of the NMMF@C cubes. Inset is a HRTEM image taken from the region indicated by a white square. (F) STEM and elemental mapping images of the Na, Mg, C, Mn, and F elements of a single NMMF@C cube.

  • Fig. 3 The deposition behavior of the Li plated on the NMMF@C-Cu.

    (A) Top and (B) cross-sectional images of Li plated with a capacity of 0.5 mAh cm−2. (C) Top and (D) cross-sectional images of Li plated with a capacity of 1 mAh cm−2. (E) Top and (F) cross-sectional images of Li plated with a capacity of 3 mAh cm−2. (G) The staged discharge curve of the NMMF@C-Cu anode and the corresponding schematic diagram of Li plating processes on the NMMF@C-Cu.

  • Fig. 4 Cryo-TEM study on the anode structure.

    (A) Morphology of Li plated on a bare Cu grid. (B and C) Morphology of Li plated on the NMMF@C-modified Cu grid. (D) Elemental mapping images of the Na, Mg, Mn, and F. (E) HRTEM and related FFT images of the SEI formed on bare Cu grid [corresponding to the white rectangular area in (A)], E (1) and E (2) correspond to regions (1) and (2) in (E), respectively. (F) HRTEM image of the SEI formed on NMMF@C-modified Cu grid [corresponding to the white rectangular area in (B)], F (1), F (2), and F (3) correspond to regions (1), (2), and (3) in (F), respectively. (G) FFT data from the image of (F), confirming the existence of LiF in the SEI layer.

  • Fig. 5 Electrochemical performance of different anodes in the half cells with the ether electrolyte.

    (A) CE versus cycle number plots of the anodes based on NMMF@C-Cu, NMMF-Cu, and b-Cu. (B) Electrochemical Li plating/stripping curves of the NMMF@C-Cu anode at 1 mA cm−2 with a specific capacity of 1 mAh cm−2. (C) Magnification of the red rectangular region in (B). (D) Galvanostatic discharge/charge voltage curves of Cu-Li and NMMF@C-Li anodes in symmetric coin cells at 1 mA cm−2.

  • Fig. 6 Electrochemical performance of full cells.

    (A) Discharge/charge voltage profiles of the NCM811/NMMF@C-Li full cell at different current densities. (B) Rate capability of the NCM811/NMMF@C-Li full cell. (C) Long-term cycling performance of NCM811/NMMF@C-Li and NCM811/Cu-Li cells at the current density of 1 C.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/6/10/eaaz3112/DC1

    Fig. S1. FESEM images of the Li plated on bare Cu foil.

    Fig. S2. FESEM images of the Li plated on the NMMF@C-Cu with the capacity of 0.5 mAh cm−2 at the current density of 0.5 mA cm−2.

    Fig. S3. FESEM images of the Li plated on the NMMF-Cu.

    Fig. S4. Characterizations of the NMMF@C cubes after soaking in the ether electrolyte (DOL/DME) for 48 hours.

    Fig. S5. XRD patterns of the NMMF@C before and after soaking in the ether electrolyte.

    Fig. S6. Characterizations of the NMMF cubes after soaking in the ether electrolyte for 48 hours.

    Fig. S7. ICP-MS results showing the concentration of various metal ions in the ether electrolyte for the same period.

    Fig. S8. The dissolution behavior of NMMF@C as a function of time in the ether electrolyte.

    Fig. S9. The initial discharge curve of the NMMF@C-Cu anode during the activation process at the current density of 50 mA g−1.

    Fig. S10. FESEM and elemental mapping images of Li plating on b-Cu with several NMMF@C particles.

    Fig. S11. A depth profiling of the elements on the Li-plated NMMF@C sample with a capacity of 0.5 mAh cm−2 by XPS sputter etching technique.

    Fig. S12. A cryo-TEM image of the Li deposited on the NMMF@C-modified Cu grid.

    Fig. S13. Cryo-TEM characterization for the M layer.

    Fig. S14. XPS characterization.

    Fig. S15. EDX characterization.

    Fig. S16. Electrochemical Li plating curves on NMMF@C-Cu anodes at 1 mA cm−2 for 1 mAh cm−2 during the 100th, 200th, 300th, 400th, and 500th cycles.

    Fig. S17. The CE versus cycle number plot of the LMA on b-Cu using NaF as the electrolyte additive.

    Fig. S18. The cycle life of the NMMF@C-Cu electrode at the current densities of 1 and 2 mA cm−2.

    Fig. S19. Morphology and electrochemical performance of the Cu electrodes with different loading thickness of NMMF@C.

    Fig. S20. The CE of Li deposition/stripping on the NMMF@C-Cu electrode at high areal capacities.

    Fig. S21. Nucleation overpotential and polarization potential.

    Fig. S22. The EIS plots of the NMMF@C-Cu and b-Cu electrodes after the 1st and 50th cycles.

    Fig. S23. Arrhenius plot of the symmetric NMMF@C-Li//NMMF@C-Li cell.

    Fig. S24. EIS plots of the symmetric cell at 1 mA cm−2 for 1 mAh cm−2.

    Fig. S25. The first charge curves of three NCM811/NMMF@C-Li full cells at the current density of 100 mA g−1.

    Fig. S26. FESEM images of the plated Li and separator in a symmetric cell after 400 cycles.

    Fig. S27. Charge/discharge curves of full cells.

    Fig. S28. Rate capability of the NCM811/Cu-Li full cell.

    Table S1. The mass loss of NMMF@C in the ether electrolyte as a function of time.

    Table S2. The comparison of the CE of the anode in our work and some reported state-of-the-art anodes tested in the DOL/DME ether electrolyte.

    References (5357)

  • Supplementary Materials

    This PDF file includes:

    • Fig. S1. FESEM images of the Li plated on bare Cu foil.
    • Fig. S2. FESEM images of the Li plated on the NMMF@C-Cu with the capacity of 0.5 mAh cm−2 at the current density of 0.5 mA cm−2.
    • Fig. S3. FESEM images of the Li plated on the NMMF-Cu.
    • Fig. S4. Characterizations of the NMMF@C cubes after soaking in the ether electrolyte (DOL/DME) for 48 hours.
    • Fig. S5. XRD patterns of the NMMF@C before and after soaking in the ether electrolyte.
    • Fig. S6. Characterizations of the NMMF cubes after soaking in the ether electrolyte for 48 hours.
    • Fig. S7. ICP-MS results showing the concentration of various metal ions in the ether electrolyte for the same period.
    • Fig. S8. The dissolution behavior of NMMF@C as a function of time in the ether electrolyte.
    • Fig. S9. The initial discharge curve of the NMMF@C-Cu anode during the activation process at the current density of 50 mA g−1.
    • Fig. S10. FESEM and elemental mapping images of Li plating on b-Cu with several NMMF@C particles.
    • Fig. S11. A depth profiling of the elements on the Li-plated NMMF@C sample with a capacity of 0.5 mAh cm−2 by XPS sputter etching technique.
    • Fig. S12. A cryo-TEM image of the Li deposited on the NMMF@C-modified Cu grid.
    • Fig. S13. Cryo-TEM characterization for the M layer.
    • Fig. S14. XPS characterization.
    • Fig. S15. EDX characterization.
    • Fig. S16. Electrochemical Li plating curves on NMMF@C-Cu anodes at 1 mA cm−2 for 1 mAh cm−2 during the 100th, 200th, 300th, 400th, and 500th cycles.
    • Fig. S17. The CE versus cycle number plot of the LMA on b-Cu using NaF as the electrolyte additive.
    • Fig. S18. The cycle life of the NMMF@C-Cu electrode at the current densities of 1 and 2 mA cm−2.
    • Fig. S19. Morphology and electrochemical performance of the Cu electrodes with different loading thickness of NMMF@C.
    • Fig. S20. The CE of Li deposition/stripping on the NMMF@C-Cu electrode at high areal capacities.
    • Fig. S21. Nucleation overpotential and polarization potential.
    • Fig. S22. The EIS plots of the NMMF@C-Cu and b-Cu electrodes after the 1st and 50th cycles.
    • Fig. S23. Arrhenius plot of the symmetric NMMF@C-Li//NMMF@C-Li cell.
    • Fig. S24. EIS plots of the symmetric cell at 1 mA cm−2 for 1 mAh cm−2.
    • Fig. S25. The first charge curves of three NCM811/NMMF@C-Li full cells at the current density of 100 mA g−1.
    • Fig. S26. FESEM images of the plated Li and separator in a symmetric cell after 400 cycles.
    • Fig. S27. Charge/discharge curves of full cells.
    • Fig. S28. Rate capability of the NCM811/Cu-Li full cell.
    • Table S1. The mass loss of NMMF@C in the ether electrolyte as a function of time.
    • Table S2. The comparison of the CE of the anode in our work and some reported state-of-the-art anodes tested in the DOL/DME ether electrolyte.
    • References (5357)

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