Research ArticleELECTROCHEMICAL ENERGY

Ultrahigh–current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF3 framework

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Science Advances  08 Sep 2017:
Vol. 3, no. 9, e1701301
DOI: 10.1126/sciadv.1701301
  • Fig. 1 Morphology of AlF3 powder and LAFN.

    (A) Sketch of AlF3 powder mesoporous framework. (B) Sketch of Al4Li9-LiF skeleton. (C) Sketch of LAFN. (D to F) SEM images of AlF3 powder under different magnifications. Scale bars, 20 μm (D), 1 μm (E), and 200 nm (F). (G to I) SEM images of pristine LAFN surface, LAFN surface after stripping 5 mA∙hour cm−2 of Li metal, and LAFN surface after stripping and plating back 5 mA∙hour cm−2 of Li metal. Scale bars, 2 μm. (J to L) Magnified SEM images of (G) to (I). Scale bars, 200 nm.

  • Fig. 2 Dendrite-suppressed, volume-stable LAFN electrode.

    (A) Sketch of ideal and nonideal plating processes due to different conductivities of the skeleton. (B and C) SEM images of Li foil surface (B) and LAFN surface (C) after one symmetric cell cycle under 1 mA cm−2 and 1 mA∙hour cm−2. Scale bars, 5 μm. (D and E) SEM images of Li foil surface (D) and LAFN surface (E) after one symmetric cell cycle under 20 mA cm−2 and 1 mA∙hour cm−2. Scale bars, 5 μm. (F to H) Cross-sectional SEM images of a pristine LAFN electrode (F), an LAFN electrode after stripping 37.5 mA∙hour cm−2 of Li (G), and an electrode after stripping and plating back 37.5 mA∙hour cm−2 of Li (H). Scale bars, 500 μm.

  • Fig. 3 Electrochemical properties of LAFN electrode.

    (A and B) Impedance performance of LAFN electrode (A) and Li foil electrode (B). (C) Voltage profile of stripping Li from LAFN electrode to 1 V versus Li+/Li. (D) XRD characterization of LAFN electrode before and after stripping Li to 1 V versus Li+/Li. arb. unit, arbitrary unit.

  • Fig. 4 Symmetric cell cycling performance of LAFN.

    (A to C) Symmetric cell cycling performance comparison between Li foil (red) and LAFN (blue) under 1 mA cm−2 (A), 10 mA cm−2 (B), and 20 mA cm−2 (C). Areal capacity was fixed at 1 mA∙hour cm−2.

  • Fig. 5 Electrochemical performance of LCO/LAFN cells.

    (A) Rate capability of LCO/LAFN cells and LCO/Li foil cells at various rates from 0.2 to 10 C. (B to D) Voltage profile comparison between LCO/LAFN cells and LCO/Li foil cells at rates of 1 C (B), 2 C (C), and 4 C (D). The dotted boxes are enlarged in fig. S23 (A to C).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/9/e1701301/DC1

    fig. S1. N2 adsorption-desorption isotherm of AlF3 powder.

    fig. S2. Fabrication of LAFN.

    fig. S3. Digital photo of 20 μl of ethylene carbonate/diethyl carbonate electrolyte dropped onto Li foil and LAFN electrode.

    fig. S4. Transmission electron microscopy characterization of pristine LAFN.

    fig. S5. Morphology of LAFN after symmetric cell cycling.

    fig. S6. Morphology of LAFN after symmetric cell cycling.

    fig. S7. Morphology of LAFN after symmetric cell cycling.

    fig. S8. Morphology of LAFN after symmetric cell cycling.

    fig. S9. Morphology of LAFN after directly plating Li metal onto its surface.

    fig. S10. EIS performance of Li foil and LAFN symmetric cells after different cycles.

    fig. S11. EIS performance of LAFN symmetric cells after stripping different percentages of capacity from one side to the other.

    fig. S12. Enlarged XRD profile of the dotted box in Fig. 3D.

    fig. S13. XPS of LAFN.

    fig. S14. Voltage profile of Li foil and LAFN symmetric cell during the 1st, 10th, 50th and 100th cycles, with a current density of 1 mA cm−2.

    fig. S15. Long-term cycling stability of LAFN electrode.

    fig. S16. Symmetric cell cycling performance of LAFN under a current density of 3 mA cm−2.

    fig. S17. Symmetric cell cycling performance of LAFN under a current density of 5 mA cm−2.

    fig. S18. Voltage plateau comparison.

    fig. S19. Symmetric cell cycling performance of LAFN under a current density of 20 mA cm−2.

    fig. S20. Symmetric cell cycling performance of LAFN under metabolic current densities.

    fig. S21. Symmetric cell cycling performance of LAFN under an areal capacity of 3 mA∙hour cm−2.

    fig. S22. Electrochemical performance of LCO/LAFN cells.

    fig. S23. Enlarged voltage profile of LCO full cell batteries.

    fig. S24. Electrochemical performance of LCO/LAFN cells.

    fig. S25. Electrochemical performance of LTO/LAFN cells.

    fig. S26. Electrochemical performance of LTO/LAFN cells for CE testing.

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. N2 adsorption-desorption isotherm of AlF3 powder.
    • fig. S2. Fabrication of LAFN.
    • fig. S3. Digital photo of 20 μl of ethylene carbonate/diethyl carbonate electrolyte dropped onto Li foil and LAFN electrode.
    • fig. S4. Transmission electron microscopy characterization of pristine LAFN.
    • fig. S5. Morphology of LAFN after symmetric cell cycling.
    • fig. S6. Morphology of LAFN after symmetric cell cycling.
    • fig. S7. Morphology of LAFN after symmetric cell cycling.
    • fig. S8. Morphology of LAFN after symmetric cell cycling.
    • fig. S9. Morphology of LAFN after directly plating Li metal onto its surface.
    • fig. S10. EIS performance of Li foil and LAFN symmetric cells after different cycles.
    • fig. S11. EIS performance of LAFN symmetric cells after stripping different percentages of capacity from one side to the other.
    • fig. S12. Enlarged XRD profile of the dotted box in Fig. 3D.
    • fig. S13. XPS of LAFN.
    • fig. S14. Voltage profile of Li foil and LAFN symmetric cell during the 1st, 10th, 50th and 100th cycles, with a current density of 1 mA cm−2.
    • fig. S15. Long-term cycling stability of LAFN electrode.
    • fig. S16. Symmetric cell cycling performance of LAFN under a current density of 3 mA cm−2.
    • fig. S17. Symmetric cell cycling performance of LAFN under a current density of 5 mA cm−2.
    • fig. S18. Voltage plateau comparison.
    • fig. S19. Symmetric cell cycling performance of LAFN under a current density of 20 mA cm−2.
    • fig. S20. Symmetric cell cycling performance of LAFN under metabolic current densities.
    • fig. S21. Symmetric cell cycling performance of LAFN under an areal capacity of 3 mA∙hour cm−2.
    • fig. S22. Electrochemical performance of LCO/LAFN cells.
    • fig. S23. Enlarged voltage profile of LCO full cell batteries.
    • fig. S24. Electrochemical performance of LCO/LAFN cells.
    • fig. S25. Electrochemical performance of LTO/LAFN cells.
    • fig. S26. Electrochemical performance of LTO/LAFN cells for CE testing.

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