Research ArticleELECTROCHEMISTRY

High-capacity aqueous zinc batteries using sustainable quinone electrodes

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Science Advances  02 Mar 2018:
Vol. 4, no. 3, eaao1761
DOI: 10.1126/sciadv.aao1761
  • Fig. 1 Quinone electrodes in aqueous ZBs.

    (A) Schematic diagram of preparing C4Q. (B) Discharge/charge voltages and capacities of selected quinone compounds (1,2-NQ, 1,4-NQ, 9,10-PQ, 9,10-AQ, and C4Q) in aqueous ZBs. The typically reported inorganic electrodes including KCuFe(CN)6 (31), Na0.95MnO2 (26), Zn3[Fe(CN)6]2 (30), FeFe(CN)6 (29), ZnMn2O4 (24), ZnxMo2.5+yVO9+z (25), Zn0.25V2O5·nH2O (23), γ-MnO2 (22), α-MnO2 (19), and Cu2+-intercalated Bi-birnessite (Bi–δ-MnO2) (27, 28) are also listed for comparison. (C) Galvanostatic discharge/charge curves of Zn-C4Q battery at the current density of 20 mA g−1. The upper x axis represents the uptake number of Zn ions. One Zn2+ with two-electron transfers generates a specific capacity of 112 mA h g−1. (D) CV curves of Zn-C4Q batteries at sweeping rates of 0.05, 0.10, 0.20, 0.30, 0.40, and 0.50 mV s−1, respectively. The reduction and oxidation peaks are linked with arrows. The inset shows the corresponding linear fit of the peak current and the square root of the scan rate.

  • Fig. 2 Deducing the active sites and structure evolution of quinone electrodes.

    The ESP- mapped molecular van der Waals surface of (A) 1,2-NQ, (B) 1,4-NQ, (C) 9,10-AQ, (D) 9,10-PQ, and (E) C4Q. Surface local minima of ESP are represented as blue spheres, and the corresponding ESP values are marked out by numbers. (F) Optimized configurations of C4Q before and after Zn ion uptake. Bottom: Corresponding configurations at different viewpoints. The distance between O–O and Zn–O has been labeled in angstroms.

  • Fig. 3 FTIR characterization of quinone electrodes.

    (A) Schematic diagram of in situ ATR-FTIR analysis. The cathode was tightly pressed on the surface of the diamond. When the IR light reflects on the surface of the cathode, it will penetrate a certain depth of sample and obtain the FTIR spectra. (B) FTIR spectra of a pristine, 1st charged, 100th charged, 200th charged, 1st discharged, 100th discharged, and 200th discharged C4Q cathode. a.u., arbitrary units. (C) In situ ATR-FTIR spectra of the C4Q cathode in one discharge/charge cycle (the current density is 20 mA g−1). The peaks at around 1650 cm−1 were assigned to the stretching vibration of carbonyls.

  • Fig. 4 Electrochemical performance optimization of aqueous Zn-C4Q batteries.

    (A) Scanning electron microscopy (SEM) images and corresponding energy dispersive x-ray spectroscopy mapping of the cross-sectional view of a Nafion membrane before (up) and after (low) electrolyte soaking. (B) Discharge/charge curves of a symmetric Zn/Nafion/Zn battery at a current density of 50 μA cm−2 and discharge/charge for 2 hours at each cycle. (C) Cycling performance of Zn-C4Q batteries with the Nafion membrane or filter paper as separators at the current density of 100 mA g−1, accompanied with the coulombic efficiency with the Nafion membrane. (D) Cycling performance of Zn-C4Q batteries and coulombic efficiency at the current density of 500 mA g−1 with a Nafion separator. (E) Galvanostatic discharge/charge curves of pouch cells. Both energy densities calculated by electrodes (C4Q cathode and theoretical Zn anode) and by the total battery have been labeled on the bottom and top of the x axis. The inset shows the packaging technology and assembled pouch cell with a standard capacity of 0.1 and 1 A · hour, respectively.

  • Fig. 5 Dissolution behavior of aqueous ZBs.

    (A) In situ UV-vis spectra of Zn-C4Q batteries with a Nafion separator. (B) In situ UV-vis spectra of Zn-C4Q batteries without a Nafion separator. These reformed batteries were discharged and charged at the current density of 100 mA g−1, and the UV-vis spectra were collected every 10 min.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/3/eaao1761/DC1

    fig. S1. Illustration of rechargeable aqueous ZBs using quinone electrodes.

    fig. S2. Electrochemical properties of other quinone compounds.

    fig. S3. LUMO energy and average discharge potential of different quinone compounds.

    fig. S4. CV curves of Zn-C4Q battery at 0.5 mV s−1 for 100 cycles.

    fig. S5. CV curves of other quinone compounds.

    fig. S6. The uptake of the fourth Zn ion in the molecular structure of C4Q.

    fig. S7. Discharge and charge curves of Zn-C4Q battery at 5 mA g−1.

    fig. S8. Raman characterizations of Zn-C4Q batteries.

    fig. S9. Ex situ XRD characterizations of Zn-C4Q batteries.

    fig. S10. TEM characterization of C4Q electrode after discharge.

    fig. S11. TEM characterization of C4Q electrode after charge.

    fig. S12. Composition of Nafion.

    fig. S13. SEM images of the prepared C4Q cathode on titanium foil.

    fig. S14. Capacity retention and zinc utilization using different loading masses of C4Q.

    fig. S15. Electrochemical performance of Zn-C4Q batteries in organic electrolyte.

    fig. S16. Digital photos of the Zn anode, separator (filter paper or Nafion membrane), and C4Q cathode after cycling.

    fig. S17. Characterization of the zinc anode after cycling using a filter paper separator.

    fig. S18. SEM images of electrodes before and after cycles.

    fig. S19. Rate performance of Zn-C4Q batteries with a Nafion separator.

    fig. S20. Galvanostatic discharge and charge curves with selected cycles at 500 mA g−1 and corresponding energy efficiency.

    fig. S21. Cycling performance of Zn-C4Q battery using C4Q cathode with a higher conductive carbon ratio (60 wt %).

    fig. S22. Exhibition of pouch cells.

    fig. S23. Digital photo and SEM image of the zinc anode after cycling in pouch cells.

    fig. S24. Digital photos of designed batteries after in situ UV-vis spectrum collections.

    fig. S25. Selected two-dimensional UV-vis spectra.

    fig. S26. 1H NMR spectra of different electrolytes after cycling in batteries used for the UV-vis test.

    fig. S27. Membrane potential tests.

    fig. S28. EIS of Zn-C4Q batteries.

    fig. S29. Electrochemical performance of aqueous Mg-C4Q batteries.

    fig. S30. Structure of C4Q after uptake of three Mg ions.

    table S1. Maximum specific capacity and lowest discharge/charge gap of electrodes coupled with metal zinc in aqueous batteries.

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Illustration of rechargeable aqueous ZBs using quinone electrodes.
    • fig. S2. Electrochemical properties of other quinone compounds.
    • fig. S3. LUMO energy and average discharge potential of different quinone compounds.
    • fig. S4. CV curves of Zn-C4Q battery at 0.5 mV s−1 for 100 cycles.
    • fig. S5. CV curves of other quinone compounds.
    • fig. S6. The uptake of the fourth Zn ion in the molecular structure of C4Q.
    • fig. S7. Discharge and charge curves of Zn-C4Q battery at 5 mA g−1.
    • fig. S8. Raman characterizations of Zn-C4Q batteries.
    • fig. S9. Ex situ XRD characterizations of Zn-C4Q batteries.
    • fig. S10. TEM characterization of C4Q electrode after discharge.
    • fig. S11. TEM characterization of C4Q electrode after charge.
    • fig. S12. Composition of Nafion.
    • fig. S13. SEM images of the prepared C4Q cathode on titanium foil.
    • fig. S14. Capacity retention and zinc utilization using different loading masses of C4Q.
    • fig. S15. Electrochemical performance of Zn-C4Q batteries in organic electrolyte.
    • fig. S16. Digital photos of the Zn anode, separator (filter paper or Nafion membrane), and C4Q cathode after cycling.
    • fig. S17. Characterization of the zinc anode after cycling using a filter paper separator.
    • fig. S18. SEM images of electrodes before and after cycles.
    • fig. S19. Rate performance of Zn-C4Q batteries with a Nafion separator.
    • fig. S20. Galvanostatic discharge and charge curves with selected cycles at 500 mA g−1 and corresponding energy efficiency.
    • fig. S21. Cycling performance of Zn-C4Q battery using C4Q cathode with a higher conductive carbon ratio (60 wt %).
    • fig. S22. Exhibition of pouch cells.
    • fig. S23. Digital photo and SEM image of the zinc anode after cycling in pouch cells.
    • fig. S24. Digital photos of designed batteries after in situ UV-vis spectrum collections.
    • fig. S25. Selected two-dimensional UV-vis spectra.
    • fig. S26. 1H NMR spectra of different electrolytes after cycling in batteries used for the UV-vis test.
    • fig. S27. Membrane potential tests.
    • fig. S28. EIS of Zn-C4Q batteries.
    • fig. S29. Electrochemical performance of aqueous Mg-C4Q batteries.
    • fig. S30. Structure of C4Q after uptake of three Mg ions.
    • table S1. Maximum specific capacity and lowest discharge/charge gap of electrodes coupled with metal zinc in aqueous batteries.

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