Research ArticleAPPLIED SCIENCES AND ENGINEERING

Ultrafast all-climate aluminum-graphene battery with quarter-million cycle life

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Science Advances  15 Dec 2017:
Vol. 3, no. 12, eaao7233
DOI: 10.1126/sciadv.aao7233
  • Fig. 1 Cathode material design and preparation.

    (A) Illustration of tricontinuous (3C, continuous electron conductor, continuous ion-conducting channel, and continuous active material) and trihigh (3H, high-quality graphene, high-orientation assembling, and high channeling) design for a desired graphene cathode. (B) Photograph of GO and rGO films. (C) Photograph of as-prepared silvery GF-HC maintaining its original integrity.

  • Fig. 2 Structure of the GF cathode.

    (A) Raman spectra of GO film (GOF), rGO film (rGF), and GF-HC exhibiting a decreasing ratio of peak intensity (ID/IG) from 0.94 for GOF and 1.17 for rGF to 0 for defect-free GF-HC. a.u., arbitrary units. (B) XPS spectra of GOF, rGF, and GF-HC exhibiting a greatly decreased oxygen concentration from 31% for GOF and 5.8% for rGF to 1.5% for GF-HC. (C) HRTEM image of GF-HC. Inset: IFFT result of the HRTEM image revealing defect-free graphene honeycomb matrix. (D) HRTEM image of GF-HC exhibiting eight neighboring few-layered graphene sheets. (E and F) Cross-sectional SEM images of GF-HC revealing hierarchically connected gasbags and channels among graphene layers. (G) Top-view SEM image of GF-HC showing fissures in the graphene layers to serve as the vertical infiltration channel. (H) Top-view SEM images of GF-Hp illustrating the absence of fissures. (I and J) Infiltration demonstration of ionic liquid electrolyte on GF-HC in a glove box, suggesting a fast infiltration process.

  • Fig. 3 Electrochemical performances.

    (A) Comparison of specific capacities between GF-HC and GF-p cathodes at 6 A g−1. (B) Overlapped charge/discharge curves of the GF-HC cathode at different cycles, exhibiting two charging plateaus of 1.7 to 2.3 V and 2.3 to 2.5 V and two discharge plateaus of 2.3 to 2.0 V and 2.0 to 1.5 V, which correspond well with cyclic voltammetry in fig. S10. (C) In situ XRD results of fully charged GF-HC, GF-p, and fully discharged GF-HC cathodes. (D) Stable specific capacities of the GF-HC cathode at ultrahigh current densities from 10 to 200 A g−1 and (E) corresponding charge/discharge curves. (F) Stable cycling performance of the GF-HC cathode at current density of 100 A g−1 within 250,000 cycles. (G and H) Comparison of rate capability and cycle life characteristics between the GF-HC cathode and various research results. Legends of (H) are also listed in (G). Detailed data are listed in table S1 (1, 2, 4, 7, 8, 15, 16, 3348). (I) Comparison of the energy/power density of Al-GB with multiple commercialized energy storage technologies and various research results (49).

  • Fig. 4 Electrochemical performances of Al-GB at different temperatures and bending state.

    (A) Specific capacities and Coulombic efficiencies of GF-HC cathodes at different temperatures from 0 to 120°C with a cutoff voltage optimization strategy. RT, room temperature. (B) Stable cycling of the GF-HC cathode at 80°C (red, 12,000 cycles) and −30°C (blue, 1000 cycles). Inset: Al-GB soft pack cells successfully igniting LED lights in ice-salt bath and 100°C oven. (C) Summary of specific capacities and rate capability of the GF-HC cathode at different temperatures below 0°C. (D) Comparison of temperature range of Al-GB with multiple commercialized energy storage technologies of Li-ion battery (LIB), aqueous supercapacitor (A-SC), and organic supercapacitor (O-SC). (E) Stable cycling of Al-GB under different bending angles, and after 10,000 folding cycles (pink), followed by 500 battery cycles under 180° bending state. The capacity retention is calculated based on the cathode (120 mAh g−1). Inset: Two bending Al-GB in series powering 65 LED lights (ignition voltage of 3.2 V) simultaneously; two flexible Al-GB serve as wearable watchband to power LED watch (ignition voltage of 3.5 V); the Al-GB watchband can still ignite red LED light for 1 min without explosion even when placed in the flame of alcohol lamp.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/12/eaao7233/DC1

    fig. S1. Additional information for cathode material design, preparation, and characterizations.

    fig. S2. Raman spectra, XRD patterns, and XPS spectra of GF-HC, GF-p, GF-Hp, and expanded graphite.

    fig. S3. HRTEM images of expanded graphite and GF-HC.

    fig. S4. SEM images of GF-HC, GF-p, and GF-Hp.

    fig. S5. Orientation demonstration of GF-HC and graphene foam with statistic of cracks in different GF cathodes.

    fig. S6. Porosity characteristics of GFs.

    fig. S7. Permeability test of ionic liquid electrolyte on GF-HC and GF-Hp in a glove box.

    fig. S8. Dynamic contact angle test of DMF droplet on different GF cathodes.

    fig. S9. Mechanical properties of GF.

    fig. S10. CV and cutoff voltage optimization of the GF-HC cathode.

    fig. S11. Cycling performances of GF-HC and GF-p.

    fig. S12. EIS and CV spectra of GF-HC, GF-p, GF-Hp, and graphite.

    fig. S13. Element mapping of the charged GF-HC cathode.

    fig. S14. Electrochemical performance of the GF-HC cathode at low rates.

    fig. S15. Charge/discharge curves of the GF-HC cathode at different temperatures.

    fig. S16. Charge/discharge curves of the GF-HC cathode and ionic conductivity of [EMIm]AlxCly ionic liquid electrolyte at low temperature.

    fig. S17. Comparison of electrochemical performances of GF-HC and GF-p cathodes at low temperature.

    fig. S18. Photograph of flexible Al-GB.

    fig. S19. EIS spectra of flexible Al-GB soft pack cell after different bending cycles.

    fig. S20. Additional information on coin cell fabrication, demonstration for the absence of side reaction, and the electrochemical performance based on mass loading.

    fig. S21. Galvanostatic cycling of the GF-HC cathode with [Et3NH]AlxCly electrolyte.

    table S1. Electrochemical properties of electrode materials from various reports.

    Calculations of AlCl4 diffusivity based on CV plot

    Calculations of AlCl4 diffusivity based on EIS data

    References (50, 51)

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. Additional information for cathode material design, preparation, and characterizations.
    • fig. S2. Raman spectra, XRD patterns, and XPS spectra of GF-HC, GF-p, GF-Hp, and expanded graphite.
    • fig. S3. HRTEM images of expanded graphite and GF-HC.
    • fig. S4. SEM images of GF-HC, GF-p, and GF-Hp.
    • fig. S5. Orientation demonstration of GF-HC and graphene foam with statistic of cracks in different GF cathodes.
    • fig. S6. Porosity characteristics of GFs.
    • fig. S7. Permeability test of ionic liquid electrolyte on GF-HC and GF-Hp in a glove box.
    • fig. S8. Dynamic contact angle test of DMF droplet on different GF cathodes.
    • fig. S9. Mechanical properties of GF.
    • fig. S10. CV and cutoff voltage optimization of the GF-HC cathode.
    • fig. S11. Cycling performances of GF-HC and GF-p.
    • fig. S12. EIS and CV spectra of GF-HC, GF-p, GF-Hp, and graphite.
    • fig. S13. Element mapping of the charged GF-HC cathode.
    • fig. S14. Electrochemical performance of the GF-HC cathode at low rates.
    • fig. S15. Charge/discharge curves of the GF-HC cathode at different temperatures.
    • fig. S16. Charge/discharge curves of the GF-HC cathode and ionic conductivity of EMImAlxCly ionic liquid electrolyte at low temperature.
    • fig. S17. Comparison of electrochemical performances of GF-HC and GF-p cathodes at low temperature.
    • fig. S18. Photograph of flexible Al-GB.
    • fig. S19. EIS spectra of flexible Al-GB soft pack cell after different bending cycles.
    • fig. S20. Additional information on coin cell fabrication, demonstration for the absence of side reaction, and the electrochemical performance based on mass loading.
    • fig. S21. Galvanostatic cycling of the GF-HC cathode with Et3NHAlxCly electrolyte.
    • table S1. Electrochemical properties of electrode materials from various reports.
    • Calculations of AlCl4 diffusivity based on CV plot
    • Calculations of AlCl4 diffusivity based on EIS data
    • References (50, 51)

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