Research ArticleBATTERIES

Artificial solid electrolyte interphase for aqueous lithium energy storage systems

See allHide authors and affiliations

Science Advances  08 Sep 2017:
Vol. 3, no. 9, e1701010
DOI: 10.1126/sciadv.1701010
  • Fig. 1 Characterizations of G-SEI.

    (A) Surface pressure versus trough area in the L-B method showing three different phases. Inset: SAED and schematics of an isotherm method and packed nanosheets in a GO film. (B to D) AFM images of 1-layer, 5-layer, and 10-layer GO films, respectively, on an HOPG substrate. AFM (E to G) and SEM (H to J) images of the Blank cathode and 5-layer and 10-layer GO films on the cathodes, respectively. Inset on the right side of (H) is the HRTEM of one LMO crystal. Arrows in (I) show the wrinkles of a GO film.

  • Fig. 2 The ReHABs performance with the G-SEI (1RGO, 5RGO, 10RGO, and 50RGO) and without the G-SEI (Blank).

    (A) CV profiles at a scan rate of 1 mV s−1. (B) Charge-discharge capacities as a function of cycle number at different C rates. (C) Charge-discharge curves of the ReHAB with the 10RGO cathode at different C rates. (D) Capacity loss (measured capacity after 1-day float charge versus initial capacity) and the corresponding float charge current density. (E) Voltage drop plateau in 72 hours of OCV tests. (F) Cyclic performance under a current density of 1 C at room temperature (25°C). (G) Corresponding charge-discharge curves at different cycles. (H) Cyclic performance of the ReHAB with the 10RGO cathode under a current density of 4 C at 60°C. (I) Corresponding charge-discharge curves.

  • Fig. 3 Impedance and Li+ diffusivity characterizations of 10RGO and Blank cathodes.

    Nyquist plots of the (A) 10RGO and (B) Blank cathodes in different cycling stages. (C and D) Rct and Li+ diffusivity of the 10RGO and Blank cathodes as a function of cycle number, respectively.

  • Fig. 4 The morphology of cathode surface, concentration of carbon, and oxidation state of the graphitic carbon particles before and after the cycling stability test.

    SEM images of the Blank (A) and 10RGO-coated (B) cathodes. (C) Raman spectra of the Blank and 1RGO and 10RGO cathodes after the cycling test. C1s (D and E) and O1s (F and G) high-resolution XPS spectra of the Blank cathode before and after the cycling test. a.u., arbitrary units. (H) Schematic of O2 and CO2 evolution and permeation on the surface and inside a RGO-coated cathode.

  • Fig. 5 Characterization of LMO cathodes before and after the cycling stability test.

    XRD (A), Raman (B), XPS Mn2p3/2 (C), and XPS Li1s (D) spectra for the Blank cathode before and after the 300 charge-discharge test in comparison with the cathodes with the G-SEI (RGO cathodes).

  • Fig. 6 Quantifying the Jahn-Teller distortion in the Blank and 10RGO cathodes.

    Lattice parameter (Δa and Δc) (A) and volume change (Δv) (B) during discharge process for the Blank and the RGO cathodes calculated from the in situ XRD patterns. (C) Schematics of the permeation-based mechanism for the Blank and RGO cathodes representing the Li+ diffusion and electron mobility.

  • Table 1 A comparison of the cycling stability of various LMO-based rechargeable lithium battery systems.

    CNT, carbon nanotubes; EC, ethylene carbonate; DMC, dimethyl carbonate; EMC, ethyl-methyl carbonate; Ppy, polypyrrole.

    CathodeAnodeElectrolyteCapacity retentionCyclesSafetyReference
    LiMn2O4VO2Saturated LiNO3 (aqueous)83%42Good(19)
    LiMn2O4TiP2O75 M LiNO3 (aqueous)85%10Good(46)
    LiMn2O4LixV2O5/Ppy5 M LiNO3 (aqueous)82%60Good(47)
    LiMn2O4/CNT hybridsZn foil2 M Li2SO4 + 1M ZnSO4 (aqueous)68%300Good(32)
    LiMn2O4LiTi2(PO4)31 M Li2SO4 (aqueous)82%200Good(48)
    LiMn2O4LiV3O82 M Li2SO4 (aqueous)53%100Good(49)
    LiMn2O4V2O5Saturated LiNO3 (aqueous)89%100Good(50)
    LiMn2O4/CNT hybridsLi foil1 M LiPF6 (EC/DMC/EMC)92%50Poor(51)
    LiMn2O4Na2V6O16·0.14H2OSaturated Li2SO4 (aqueous)77%200Good(52)
    Porous LiMn2O4 spheresMetallic lithium1 M LiPF6 (EC/DMC)73%1000Poor(53)
    AlF3-coated LiMn2OZn foil1 M Li2SO490%100Good(54)
    LiMn2O4Zn foilThixotropic gel61%1000Good(55)
    LiMn2O4Zn foilPb2+-containing gel75%300Good(56)
    LiMn2O4 electrode with RGO films as G-SEIZn foil1 M Li2SO4 + 2M ZnSO4 (aqueous)87%
    73% (measured at 60°C)
    600
    100
    GoodThis work

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/9/e1701010/DC1

    fig. S1. Characterizations of graphite, GO, and RGO.

    fig. S2. XRD patterns of the Blank cathode treated with hydrazine.

    fig. S3. Contact angle measurement results of the hydrazine aqueous solution on the GO-coated and Blank cathodes.

    fig. S4. SEM image of the 10RGO cathode obtained by 10 times layer-by-layer deposition of 1RGO.

    fig. S5. Rate capability results of the battery with the 10GO cathode (without hydrazine reduction) in comparison with the Blank cathode.

    fig. S6. Typical charge-discharge curves of ReHAB with the 10RGO cathode at 0.2 C.

    fig. S7. Capacity loss after 1-day float charge of the cathodes with different thicknesses of the G-SEI (1RGO, 5RGO, and 10RGO) and Blank cathodes (dip-coating GO and in situ reduction to RGO).

    fig. S8. Capacity loss after 1-day float charge of the 1RGO, 5RGO, 10RGO, and Blank cathodes (directly dip-coating RGO).

    fig. S9. Rate capability results of the pristine LMO and RGO-coated LMO particles in the cathode.

    fig. S10. Capacity loss after 1-day float charge and rate capabilities of Blank and 10RGO (thermally reduced) cathodes.

    fig. S11. The inside and outside of a large-scale battery cell (7 mA·hour) with 9-cm2 cathode surface area for potential applications in the UPS power sources.

    fig. S12. Capacity loss after 1-day float charge of the 1RGO, 5RGO, 10RGO, and Blank cathodes in the large-scale cell (fig. S10) (mass loading of active materials, 25 to 28 mg cm−2; L-S method to coat GO followed by water vapor reduction).

    fig. S13. Typical charge-discharge curves of the 10RGO-LMO/AC asymmetrical supercapacitor at different current densities.

    fig. S14. Cycling stability of the 10RGO-LMO/AC asymmetrical supercapacitor at a current density of 4 A g−1.

    fig. S15. Relevant equivalent circuit model for EIS data in Fig. 3.

    fig. S16. Rct of the 10RGO and Blank cathodes as a function of time without repeated cycles.

    fig. S17. Rs of the 10RGO and Blank cathodes as a function of repeated cycles of charge-discharge.

    fig. S18. Rs of the 10RGO and Blank cathodes as a function of time without repeated cycles.

    fig. S19. O1s peaks of the 10RGO cathode after the cycling test on the surface (red) and inside the bulk (blue).

    fig. S20. Coulombic efficiencies of the 10RGO and Blank samples during 300 cycles at 4 C.

    fig. S21. In situ XRD patterns of Blank and 10RGO cathode during discharge process (LixMn2O4, 0.11 < x < 1).

    fig. S22. Contact angle results of the aqueous electrolytes on the Blank (left) and 10RGO (right) cathodes.

    fig. S23. The cycling properties of the Blank and 10RGO cathodes that are made of inactive silica particles rather than the LMO.

    fig. S24. Discharge curves of the 10RGO/silica cathode at a current density of 16 mA g−1.

    fig. S25. Typical CVs of the 10RGO cathode at a scan rate of 0.1 to 0.7 mV s−1.

    fig. S26. The peak current (ip) in the 10RGO cathode samples (peak 1 in this study) as a function of the square root of the scan rate (v).

    Calculations of Li+ diffusivity based on EIS data

    Calculations of Li+ diffusivity based on CV plot

    Reference (90)

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Characterizations of graphite, GO, and RGO.
    • fig. S2. XRD patterns of the Blank cathode treated with hydrazine.
    • fig. S3. Contact angle measurement results of the hydrazine aqueous solution on the GO-coated and Blank cathodes.
    • fig. S4. SEM image of the 10RGO cathode obtained by 10 times layer-by-layer deposition of 1RGO.
    • fig. S5. Rate capability results of the battery with the 10GO cathode (without hydrazine reduction) in comparison with the Blank cathode.
    • fig. S6. Typical charge-discharge curves of ReHAB with the 10RGO cathode at 0.2 C.
    • fig. S7. Capacity loss after 1-day float charge of the cathodes with different thicknesses of the G-SEI (1RGO, 5RGO, and 10RGO) and Blank cathodes (dip-coating GO and in situ reduction to RGO).
    • fig. S8. Capacity loss after 1-day float charge of the 1RGO, 5RGO, 10RGO, and Blank cathodes (directly dip-coating RGO).
    • fig. S9. Rate capability results of the pristine LMO and RGO-coated LMO particles in the cathode.
    • fig. S10. Capacity loss after 1-day float charge and rate capabilities of Blank and 10RGO (thermally reduced) cathodes.
    • fig. S11. The inside and outside of a large-scale battery cell (7 mA·hour) with 9-cm2 cathode surface area for potential applications in the UPS power sources.
    • fig. S12. Capacity loss after 1-day float charge of the 1RGO, 5RGO, 10RGO, and Blank cathodes in the large-scale cell (fig. S10) (mass loading of active materials, 25 to 28 mg cm−2; L-S method to coat GO followed by water vapor reduction).
    • fig. S13. Typical charge-discharge curves of the 10RGO-LMO/AC asymmetrical supercapacitor at different current densities.
    • fig. S14. Cycling stability of the 10RGO-LMO/AC asymmetrical supercapacitor at a current density of 4 A g−1.
    • fig. S15. Relevant equivalent circuit model for EIS data in Fig. 3.
    • fig. S16. Rct of the 10RGO and Blank cathodes as a function of time without repeated cycles.
    • fig. S17. Rs of the 10RGO and Blank cathodes as a function of repeated cycles of charge-discharge.
    • fig. S18. Rs of the 10RGO and Blank cathodes as a function of time without repeated cycles.
    • fig. S19. O1s peaks of the 10RGO cathode after the cycling test on the surface (red) and inside the bulk (blue).
    • fig. S20. Coulombic efficiencies of the 10RGO and Blank samples during 300 cycles at 4 C.
    • fig. S21. In situ XRD patterns of Blank and 10RGO cathode during discharge process (LixMn2O4, 0.11 < x < 1).
    • fig. S22. Contact angle results of the aqueous electrolytes on the Blank (left) and 10RGO (right) cathodes.
    • fig. S23. The cycling properties of the Blank and 10RGO cathodes that are made of inactive silica particles rather than the LMO.
    • fig. S24. Discharge curves of the 10RGO/silica cathode at a current density of 16 mA g−1.
    • fig. S25. Typical CVs of the 10RGO cathode at a scan rate of 0.1 to 0.7 mV s−1.
    • fig. S26. The peak current (ip) in the 10RGO cathode samples (peak 1 in this study) as a function of the square root of the scan rate (v).
    • Calculations of Li+ diffusivity based on EIS data
    • Calculations of Li+ diffusivity based on CV plot
    • Reference (90)

    Download PDF

    Files in this Data Supplement: