Research ArticleELECTROCHEMISTRY

Ultralong cycle stability of aqueous zinc-ion batteries with zinc vanadium oxide cathodes

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Science Advances  04 Oct 2019:
Vol. 5, no. 10, eaax4279
DOI: 10.1126/sciadv.aax4279
  • Fig. 1 Structural and morphological characterization of the VOOH nanospheres.

    (A) XRD pattern, (B) SEM image, (C) TEM image, (D) selected area electron diffraction, (E) high-resolution TEM image of the VOOH nanospheres, and (F) V 2p and O 1s XPS spectra. a.u., arbitrary units.

  • Fig. 2 Aqueous phase transition from VOOH nanospheres to hierarchically porous ZVO nanoflowers.

    (A) Typical charge/discharge profiles for the initial 10 cycles in 3 M Zn(CF3SO3)2 aqueous electrolyte at a rate of 0.2 A g−1. (B) CV curves of VOOH electrode at a scan rate of 0.2 mV s−1 in the voltage range of 0.3 to 1.6 V. (C) XRD patterns of VOOH electrode at selected states during the first cycle. (D) XRD patterns of VOOH electrode at different cycling stages. SUS, steel use stainless.

  • Fig. 3 Morphological and compositional characterization of the ZVO electrode during charge/discharge.

    (A) SEM image, (B) TEM image, and (C) STEM image and corresponding STEM-EDS elemental mapping images of the fully charged ZVO electrode. (D) SEM image and (E and F) STEM image and corresponding STEM-EDS elemental mapping images of the fully discharged ZVO electrode.

  • Fig. 4 Electrochemical mechanism studies.

    (A) Ex situ XRD patterns of the ZVO electrode at different charge/discharge states as indicated in (B). (B) Corresponding charge/discharge curves at 0.2 A g−1 in 3 M Zn(CF3SO3)2 aqueous electrolyte. Ex situ high-resolution XPS spectra of the (C) Zn 2p region of pristine VOOH, fully discharged and charged ZVO electrodes. (D to F) V 2p region of pristine, fully discharged and charged ZVO electrodes.

  • Fig. 5 Electrochemical behaviors of Zn/ZVO batteries with 3 M Zn(CF3SO3)2 aqueous electrolyte.

    (A) Galvanostatic charge/discharge profiles for ZVO electrodes at various current densities. (B) Rate capability of ZVO electrodes. (C) Cycling performance at 0.2 A g−1. (D) CV curves of ZVO electrodes at different scan rates. (E) Corresponding plots of log(i) versus log(v) at cathodic and anodic peaks. (F) Ragone plot of Zn/ZVO cell in comparison with other aqueous ZIBs. (G) Long-term cycling performance at 10 A g−1.

  • Fig. 6 Proof of excellent long-term cycling stability.

    Ex situ high-resolution TEM images of the ZVO electrode (A) at fully charged (1.6 V) and (B) discharged state (0.3 V). (C) Solid-state 1H nuclear magnetic resonance (NMR) spectra of the fully charged and discharged ZVO electrode. The sharp peak at 4.09 ppm belongs to the structural water. The broad shoulder at 4.14 ppm in the fully discharged ZVO likely represents the hydronium. (D to L) SEM images of the cathode after nth cycles.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/10/eaax4279/DC1

    Fig. S1. EDS mapping and elemental analysis of the as-obtained VOOH.

    Fig. S2. Discharge capacities of VOOH nanospheres in 3 M Zn(CF3SO3)2 aqueous electrolyte at a rate of 0.2 A g−1.

    Fig. S3. Morphological evolution of the VOOH cathode during the first cycle in 3 M Zn(CF3SO3)2 electrolyte at 0.2 A g−1.

    Fig. S4. EDS mapping and elemental analysis of the electrode after the first discharge.

    Fig. S5. Schematic illustration of the aqueous phase transition from VOOH to ZVO electrode during electrochemical charge and discharge processes.

    Fig. S6. Eletrochemical performance of VOOH electrodes in organic 0.2 M Zn(CF3SO3)2/acetonitrile electrolyte at 0.2 A g−1.

    Fig. S7. XRD pattern and SEM image of the VOOH cathode after the electrochemical cycling in organic 0.2 M Zn(CF3SO3)2/acetonitrile electrolyte.

    Fig. S8. The cycling/electrochemical performance of Zn/VOOH cells in ZnSO4 electrolyte with different concentrations (1 to 3 M) at 0.2 A g−1.

    Fig. S9. Comparison of the cycling/electrochemical performance of Zn/VOOH cells with different concentrations (1 to 3 M) of Zn(CF3SO3)2 electrolyte at 0.2 A g−1.

    Fig. S10. Nitrogen adsorption-desorption isotherm and the Barrett-Joyner-Halenda pore size distribution plot of the hierarchical ZVO.

    Fig. S11. TEM-EDS analysis of fully charged/discharged ZVO nanoflower cathode.

    Fig. S12. TGA curve of the hierarchical ZVO nanoflowers under nitrogen atmosphere at a heat ramp of 10°C /min.

    Fig. S13. Comparison of typical charge/discharge curves and cycling performance of ZVO electrodes in different electrolytes.

    Fig. S14. Comparison of Nyquist plots of Zn/ZVO cells in different electrolytes.

    Fig. S15. SEM images of the pristine and cycled Zn anode at 10 A g−1.

    Fig. S16. XRD patterns of the pristine and cycled Zn anodes.

    Fig. S17. EIS spectra of Zn/ZVO cell after 1st, 5th, and 10th cycles at 0.2 A g−1 in 3 M Zn(CF3SO3)2 aqueous electrolyte.

    Fig. S18. Nyquist plots of Zn/ZVO cells at fully charged state in 3 M ZnSO4 and 3 M Zn(CF3SO3)2 electrolyte.

    Fig. S19. Charge-discharge GITT profiles for the ZVO cathode and the corresponding Zn2+ diffusion coefficient (D).

    Fig. S20. Long-term cycling performance of Zn/ZVO batteries at various current densities.

    Fig. S21. Ex situ XRD patterns of the cycled ZVO electrode at 10 A g−1.

    Table S1. ICP-AES analysis of ZVO at fully charged state.

    Table S2. Comparison of electrochemical performance of different cathode materials for aqueous Zn-ion batteries.

  • Supplementary Materials

    This PDF file includes:

    • Fig. S1. EDS mapping and elemental analysis of the as-obtained VOOH.
    • Fig. S2. Discharge capacities of VOOH nanospheres in 3 M Zn(CF3SO3)2 aqueous electrolyte at a rate of 0.2 A g−1.
    • Fig. S3. Morphological evolution of the VOOH cathode during the first cycle in 3 M Zn(CF3SO3)2 electrolyte at 0.2 A g−1.
    • Fig. S4. EDS mapping and elemental analysis of the electrode after the first discharge.
    • Fig. S5. Schematic illustration of the aqueous phase transition from VOOH to ZVO electrode during electrochemical charge and discharge processes.
    • Fig. S6. Electrochemical performance of VOOH electrodes in organic 0.2 M Zn(CF3SO3)2/acetonitrile electrolyte at 0.2 A g−1.
    • Fig. S7. XRD pattern and SEM image of the VOOH cathode after the electrochemical cycling in organic 0.2 M Zn(CF3SO3)2/acetonitrile electrolyte.
    • Fig. S8. The cycling/electrochemical performance of Zn/VOOH cells in ZnSO4 electrolyte with different concentrations (1 to 3 M) at 0.2 A g−1.
    • Fig. S9. Comparison of the cycling/electrochemical performance of Zn/VOOH cells with different concentrations (1 to 3 M) of Zn(CF3SO3)2 electrolyte at 0.2 A g−1.
    • Fig. S10. Nitrogen adsorption-desorption isotherm and the Barrett-Joyner-Halenda pore size distribution plot of the hierarchical ZVO.
    • Fig. S11. TEM-EDS analysis of fully charged/discharged ZVO nanoflower cathode.
    • Fig. S12. TGA curve of the hierarchical ZVO nanoflowers under nitrogen atmosphere at a heat ramp of 10°C /min.
    • Fig. S13. Comparison of typical charge/discharge curves and cycling performance of ZVO electrodes in different electrolytes.
    • Fig. S14. Comparison of Nyquist plots of Zn/ZVO cells in different electrolytes.
    • Fig. S15. SEM images of the pristine and cycled Zn anode at 10 A g−1.
    • Fig. S16. XRD patterns of the pristine and cycled Zn anodes.
    • Fig. S17. EIS spectra of Zn/ZVO cell after 1st, 5th, and 10th cycles at 0.2 A g−1 in 3 M Zn(CF3SO3)2 aqueous electrolyte.
    • Fig. S18. Nyquist plots of Zn/ZVO cells at fully charged state in 3 M ZnSO4 and 3 M Zn(CF3SO3)2 electrolyte.
    • Fig. S19. Charge-discharge GITT profiles for the ZVO cathode and the corresponding Zn2+ diffusion coefficient (D).
    • Fig. S20. Long-term cycling performance of Zn/ZVO batteries at various current densities.
    • Fig. S21. Ex situ XRD patterns of the cycled ZVO electrode at 10 A g−1.
    • Table S1. ICP-AES analysis of ZVO at fully charged state.
    • Table S2. Comparison of electrochemical performance of different cathode materials for aqueous Zn-ion batteries.

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