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An ultrafast rechargeable aluminium-ion battery

Subjects

Abstract

The development of new rechargeable battery systems could fuel various energy applications, from personal electronics to grid storage1,2. Rechargeable aluminium-based batteries offer the possibilities of low cost and low flammability, together with three-electron-redox properties leading to high capacity3. However, research efforts over the past 30 years have encountered numerous problems, such as cathode material disintegration4, low cell discharge voltage (about 0.55 volts; ref. 5), capacitive behaviour without discharge voltage plateaus (1.1–0.2 volts6 or 1.8–0.8 volts7) and insufficient cycle life (less than 100 cycles) with rapid capacity decay (by 26–85 per cent over 100 cycles)4,5,6,7. Here we present a rechargeable aluminium battery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode. The battery operates through the electrochemical deposition and dissolution of aluminium at the anode, and intercalation/de-intercalation of chloroaluminate anions in the graphite, using a non-flammable ionic liquid electrolyte. The cell exhibits well-defined discharge voltage plateaus near 2 volts, a specific capacity of about 70 mA h g–1 and a Coulombic efficiency of approximately 98 per cent. The cathode was found to enable fast anion diffusion and intercalation, affording charging times of around one minute with a current density of ~4,000 mA g–1 (equivalent to ~3,000 W kg–1), and to withstand more than 7,500 cycles without capacity decay.

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Figure 1: Rechargeable Al/graphite cell.
Figure 2: An ultrafast and stable rechargeable Al/graphite cell.
Figure 3: Al/graphite cell reaction mechanisms.
Figure 4: Chemical probing of a graphitic cathode by XPS and AES.

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Acknowledgements

We thank M. D. Fayer for discussions. We also thank Y. Cui’s group for use of an argon-filled glove box and a vacuum oven. M.-C.L thanks the Bureau of Energy, Ministry of Economic Affairs, Taiwan, for supporting international cooperation between Stanford University and ITRI. B.L. acknowledges support from the National Natural Science Foundation of China (grant no. 21303046), the China Scholarship Council (no. 201308430178), and the Hunan University Fund for Multidisciplinary Developing (no. 531107040762). We also acknowledge support from the US Department of Energy for novel carbon materials development and electrical characterization work (DOE DE-SC0008684), Stanford GCEP, the Precourt Institute of Energy, and the Global Networking Talent 3.0 plan (NTUST 104DI005) from the Ministry of Education of Taiwan.

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Authors

Contributions

M.-C.L., M.G., B.L. and Y.W. contributed equally to this work. M.-C.L. and H.D. conceived the idea for the project. B.L. prepared the graphitic foam. M.-C.L., M.G., B.L., Y.W., D.-Y.W., M.A. and M. Guan performed electrochemical experiments. M.-C.L., C.C. and J.Y conducted in situ Raman spectroscopy measurements. M.-C.L., M.G., B.L. and Y.W. performed ex situ X-ray diffraction measurements. M.G., M.-C.L., B.L. and Y.W. performed X-ray photoelectron spectroscopy and Auger electron spectroscopy measurements. M.-C.L., M.G., B.L., Y.W., D.-Y.W., M.A., B.-J.H. and H.D. discussed the results, analysed the data and drafted the manuscript.

Corresponding author

Correspondence to Hongjie Dai.

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Competing interests

The authors declare no competing financial interests.

Extended data figures and tables

Extended Data Figure 1 X-ray diffraction patterns of graphitic cathode materials.

The natural graphite, pyrolytic graphite (PG) and graphitic foam exhibited typical graphite structure, with a sharp (002) X-ray diffraction (XRD) graphite peak at 2θ ≈ 26.55° (d spacing = 3.35 Å).

Extended Data Figure 2 Determination of the optimal mole ratio of AlCl3/[EMIm]Cl ionic liquid electrolyte.

a, Galvanostatic charge and discharge curves of Al/PG cells at a current density of 66 mA g−1 in various mole ratios (1.1, 1.3, 1.5 and 1.8) of AlCl3/[EMIm]Cl ionic liquid electrolytes in a Swagelok-type cell. The Coulombic efficiencies of the cells are shown in parentheses. b, Raman spectrum of the ionic liquid electrolyte with a mole ratio of AlCl3/[EMIm]Cl = 1.3.

Extended Data Figure 3 Calculated discharging capacities of Al/graphite cells with different masses of graphitic materials.

a, Natural graphite foils of 50 μm and 130 μm thickness; b, PG and graphitic foam. These data suggest that the entire graphitic material (natural graphite, PG and graphitic foam) participated in the cell cathode reaction.

Extended Data Figure 4 Galvanostatic charge and discharge curves of an Al/PG cell.

The cell was constructed with one layer of glass fibre separator and 0.08 ml of ionic liquid electrolyte, suggesting that the minimum amount of electrolyte could be 0.02 ml per mg of PG. This electrochemical study was performed in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl = 1.3 (by mole) at a current density of 66 mA g−1 in a Swagelok-type cell.

Extended Data Figure 5 Surface observations of an Al anode.

a, b, SEM images of the Al anode obtained from two Al/PG cells after 20 (a) and 100 (b) cycles, respectively, and indicate no dendrite formation over these cycles. Scale bars, 10 μm.

Extended Data Figure 6 Electrochemical stability of the AlCl3/[EMIm]Cl ionic liquid electrolyte.

a, Galvanostatic curves of Al/PG cells with different cut-off charge voltages obtained at 66 mA g−1 in a Swagelok-type cell. b, Cyclic voltammetry curve of a Al/glassy carbon (GC) cell at 10 mV s−1 in a Swagelok-type cell. c, d, Stability test of Al/natural graphite pouch cell at 66 mA g−1 in electrolytes containing water at 7,500–10,000 p.p.m. (c) and 500–700 p.p.m. (d). The Coulombic efficiencies are respectively 95.2% and 98.6%, and the discharge capacities are respectively 54.9 and 61.8 mA h g−1 at the 15 cycle. e, Gas chromatography spectrum of gaseous samples withdrawn from Al/graphite cells after 30 cycles using electrolyte with 7,500–10,000 p.p.m. H2O content. The peak found in the retention time at ~0.5 min corresponds to hydrogen gas and matches the retention time of pure hydrogen gas used for calibration.

Extended Data Figure 7 Rate capability of an Al/PG cell.

a, Capacity retention of an Al/PG cell cycled at various current densities, showing good cycling stability at different charge–discharge current densities. b, Coulombic efficiency versus current density data of Al/PG cells, indicating the Coulombic efficiency is ~95–97% at current densities of 66–132 mA g−1. Error bars, standard deviation from the Coulombic efficiency for each current density. All electrochemical studies were performed in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl = 1.3 (by mole) in a Swagelok-type cell.

Extended Data Figure 8 Advantages of PG as the cathode for an Al/graphite cell.

a, b, Right: photographs of natural graphite (a) and pyrolytic graphite (PG; b) before and after being fully charged in an AlCl3/[EMIm]Cl = 1.3 (by mole) ionic liquid electrolyte. Scale bars, 1 cm. Left: the schematic plots indicate the chemical bonds between the graphene sheets of natural graphite (Vander Waals bonding) and of PG (covalent bonding). c, Galvanostatic charge and discharge curves of an Al/PG cell (at 66 mA g−1) and an Al/natural graphite cell (at 33 mA g−1) in an ionic liquid electrolyte of composition AlCl3/[EMIm]Cl = 1.3 (by mole) in a Swagelok-type cell.

Extended Data Figure 9 Rate capability of an Al/graphitic-foam cell.

a, Capacity retention of an Al/graphitic-foam cell cycled at various current densities, showing cycling stability at different charge–discharge current densities. All electrochemical studies were performed in an AlCl3/[EMIm]Cl = 1.3 (by mole) ionic liquid electrolyte in a pouch cell. b, Galvanostatic charge and discharge curves of Al/graphitic-foam cells charging at 5,000 mA g−1 and discharging at various current densities ranging from 100 to 5,000 mA g−1. Same electrolyte and cell type as a.

Extended Data Figure 10 Reaction mechanism of graphitic cathodes.

a, In situ Raman spectra recorded for the graphitic-foam cathode through a charge/discharge cycle showing chloroaluminate anion intercalation/de-intercalation into graphite. b, Ex situ XRD patterns of the pristine and fully charged (62 mA h g−1) graphitic foam. c, EDS spectrum of as-calcined fully charged (62 mA h g−1) PG at 850 °C in air. d, Cyclic voltammetry curves of Al foil and PG at a scan rate of 10 mV s−1 against an Al reference electrode.

Supplementary information

Supplementary Text

This file contains Supplementary Text, which relates to Supplementary Videos 1 and 2. (PDF 112 kb)

A flexible Al/pyrolytic graphite cell continuously powers a red LED under a continuous bending and non-bending condition.

A flexible Al/pyrolytic graphite cell continuously powers a red LED (operating voltage ~1.7V) under a continuous bending and non-bending condition. (MP4 27476 kb)

An Al/prolytic graphite cell was drilled through without causing safety hazard due to the high stability of ionic liquid electrolyte without flammability in air.

An Al/prolytic graphite cell was drilled through without causing safety hazard (only slight temperature variation, see temperature meter on the left) due to the high stability of ionic liquid electrolyte without flammability in air. Also, the cell operation continued (see voltage meter on the right) to light a red LED. (MPG 17200 kb)

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Lin, MC., Gong, M., Lu, B. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015). https://doi.org/10.1038/nature14340

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