Research ArticleELECTRICAL ENGINEERING

Quasi–solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes

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Science Advances  01 Feb 2017:
Vol. 3, no. 2, e1602396
DOI: 10.1126/sciadv.1602396
  • Fig. 1 Optimal characterization of CPE.

    (A) The composition of CPE. Inset: Transmission electron microscopy (TEM) image of fumed SiO2. (B) Ionic conductivity of CPE with different contents of fumed SiO2. (C) Scanning electron microscopy (SEM) images of CPE with a thickness of 160 μm. Inset: SEM image of an enlarged view. (D) Atomic force microscopy (AFM) image of CPE with 3D view. (E) AFM images of Young modulus mapping. (F) Inflammability test of CPE before loading with liquid electrolyte. Fire from a lighter is ~500°C. (G) Thermal gravity analysis and heat flow curves of CPE and glass fiber, both of which are holding liquid electrolyte of TEGDME.

  • Fig. 2 Design and characterization of rGO-Na anode.

    (A to C) SEM images with corresponding inset photographs of GO foam (A), rGO foam reduced by molten Na (B), and rGO-Na anode surface (C). (D) FTIR of GO foam and rGO foam. a.u., arbitrary units. XPS spectra of O1s (E) and C1s (F) of GO foam and rGO foam. (G) XRD of rGO and rGO-Na anode. (H) Cyclic voltammograms of Na+ plating/stripping in a rGO-Na or Na/CPE/stainless steel cell with a sweep speed of 0.5 V s−1. (I) Fast discharge/charge profiles of quasi–solid state Na-CO2 batteries in Ar atmosphere using rGO-Na and pure Na anodes. Rate, 0.3 mA cm−2; voltage range, 1 to 4 V. Inset: SEM images of rGO-Na and pure Na anode surfaces after 450 cycles.

  • Fig. 3 Synthesis and characterization of a-MCNT cathodes.

    Raman (A) and FTIR (B) comparison of pristine MCNTs and a-MCNTs. The optimized geometries and corresponding adsorption energies of CO2 adsorbed on MCNTs (C) and a-MCNTs (D). SEM (E and F) and TEM (G) images of a-MCNT cathodes. The porous structure of cross-linking a-MCNTs offers open channels for CO2 transfer.

  • Fig. 4 The performance of quasi–solid state Na-CO2 batteries with rGO-Na anodes.

    (A) Rate capability. Insets: SEM images of discharged products at different rates. The black, red, blue, and green scale bars correspond to rates of 100, 200, 300, and 500 mA g−1, respectively. (B) Discharge/charge profiles and (C) corresponding variation of the terminal discharge voltage with a cutoff capacity of 1000 mA·hour g−1 at 200 mA g−1. (D) Initial discharge/charge profiles in SCE with different CO2 partial pressure. Rate, 50 mA g−1. Four bottles use different test conditions. #1, SCE atmosphere with PVDF film protection; #2, dry SCE with 50% CO2 and 50% N2; #3, dry SCE with 10% CO2 and 90% N2; #4, dry SCE with 5% CO2 and 95% N2. (E) A photograph of pouch-type battery (20 × 20 cm2, 10 g) packed in a plastic bag with two stainless steel plates (25 × 25 cm2) to fix. (F) Discharge/charge profiles at 10 mA with a reversible capacity of 200 mA·hour. Inset: Corresponding variation of the middle discharge voltage.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/2/e1602396/DC1

    Chemicals and materials

    Fabrication of curly carbon nanosheets

    Material characterization

    Battery assembly

    Electrochemical test

    CO2 evolution test

    Energy density calculation

    Density function theory (DFT) calculation

    Explanatory calculation

    fig. S1. The raw materials and synthesis procedures of CPE.

    fig. S2. The optimization of Na+-CPE.

    fig. S3. The pore size distribution of CPE.

    fig. S4. The CO2 diffusion test.

    fig. S5. SEM images of CPE surface.

    fig. S6. Roughness and Young modulus of polymer matrix (PVDF-HFP/4% SiO2) of CPE.

    fig. S7. Leakage test of Na-CO2 batteries.

    fig. S8. Inflammability test of polymer matrix (PVDF-HFP/SiO2) of CPE.

    fig. S9. Raman of CPE, polymer matrix, and liquid electrolyte.

    fig. S10. Transporting mechanism of Na+ in polymer chains and work window of CPE.

    fig. S11. Long-term stability analysis of CPE.

    fig. S12. Element mapping and XPS-Na1s of rGO-Na anode.

    fig. S13. Mechanical strength and toughness of pure Na and rGO-Na anodes.

    fig. S14. Anode analysis.

    fig. S15. Galvanostatic cycling of a symmetric rGO-Na electrodes and pure Na anodes.

    fig. S16. The optimized geometries of CO2 adsorbed on MCNT and a-MCNTs.

    fig. S17. Soluble inflation of MCNTs and a-MCNTs toward TEGDME solvent.

    fig. S18. Initial discharge and charge profiles of Na-CO2 batteries with the configuration of Na/NaClO4-TEGDME/cathode.

    fig. S19. Reaction mechanism analysis of Na-CO2 batteries.

    fig. S20. Discharge product analysis of quasi–solid state Na-CO2 battery.

    fig. S21. SEM image of a-MCNT cathode with discharge capacity of 0.1 mA·hour at 100 mA g−1.

    fig. S22. Full discharge and charge of quasi–solid state Na-CO2 batteries.

    fig. S23. Characterizations of curly carbon nanosheets.

    fig. S24. Discharge/charge curves of quasi–solid state Na-CO2 batteries with new carbon cathodes that contain curly carbon nanosheets.

    fig. S25. A device for SCE.

    fig. S26. Discharge/charge profiles in SCE with PVDF film protection of quasi–solid state Na-CO2 batteries.

    fig. S27. Discharge/charge profiles of quasi–solid state Na-CO2 batteries at 50°C.

    fig. S28. The preparation and assembly of large batteries.

    fig. S29. Pouch-type battery performance.

    table S1. Battery performance comparison.

    movie S1. Sudden reaction on GO foam.

    movie S2. Molten Na infusion into rGO foam.

    References (3141)

  • Supplementary Materials

    This PDF file includes:

    • Chemicals and materials
    • Fabrication of curly carbon nanosheets
    • Material characterization
    • Battery assembly
    • Electrochemical test
    • CO2 evolution test
    • Energy density calculation
    • Density function theory (DFT) calculation
    • Explanatory calculation
    • fig. S1. The raw materials and synthesis procedures of CPE.
    • fig. S2. The optimization of Na+-CPE.
    • fig. S3. The pore size distribution of CPE.
    • fig. S4. The CO2 diffusion test.
    • fig. S5. SEM images of CPE surface.
    • fig. S6. Roughness and Young modulus of polymer matrix (PVDF-HFP/4% SiO2) of CPE.
    • fig. S7. Leakage test of Na-CO2 batteries.
    • fig. S8. Inflammability test of polymer matrix (PVDF-HFP/SiO2) of CPE.
    • fig. S9. Raman of CPE, polymer matrix, and liquid electrolyte.
    • fig. S10. Transporting mechanism of Na+ in polymer chains and work window of CPE.
    • fig. S11. Long-term stability analysis of CPE.
    • fig. S12. Element mapping and XPS-Na1s of rGO-Na anode.
    • fig. S13. Mechanical strength and toughness of pure Na and rGO-Na anodes.
    • fig. S14. Anode analysis.
    • fig. S15. Galvanostatic cycling of a symmetric rGO-Na electrodes and pure Na anodes.
    • fig. S16. The optimized geometries of CO2 adsorbed on MCNT and a-MCNTs.
    • fig. S17. Soluble inflation of MCNTs and a-MCNTs toward TEGDME solvent.
    • fig. S18. Initial discharge and charge profiles of Na-CO2 batteries with the configuration of Na/NaClO4-TEGDME/cathode.
    • fig. S19. Reaction mechanism analysis of Na-CO2 batteries.
    • fig. S20. Discharge product analysis of quasi–solid state Na-CO2 battery.
    • fig. S21. SEM image of a-MCNT cathode with discharge capacity of 0.1 mA∙hour at 100 mA g−1.
    • fig. S22. Full discharge and charge of quasi–solid state Na-CO2 batteries.
    • fig. S23. Characterizations of curly carbon nanosheets.
    • fig. S24. Discharge/charge curves of quasi–solid state Na-CO2 batteries with new carbon cathodes that contain curly carbon nanosheets.
    • fig. S25. A device for SCE.
    • fig. S26. Discharge/charge profiles in SCE with PVDF film protection of quasi–solid state Na-CO2 batteries.
    • fig. S27. Discharge/charge profiles of quasi–solid state Na-CO2 batteries at 50°C.
    • fig. S28. The preparation and assembly of large batteries.
    • fig. S29. Pouch-type battery performance.
    • table S1. Battery performance comparison.
    • Legends for movies S1 and S2
    • References (31–41)

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    Other Supplementary Material for this manuscript includes the following:

    • movie S1 (.mp4 format). Sudden reaction on GO foam.
    • movie S2 (.avi format). Molten Na infusion into rGO foam.

    Files in this Data Supplement:

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