Rechargeable aluminium organic batteries


Since aluminium is one of the most widely available elements in Earth’s crust, developing rechargeable aluminium batteries offers an ideal opportunity to deliver cells with high energy-to-price ratios. Nevertheless, finding appropriate host electrodes for insertion of aluminium (complex) ions remains a fundamental challenge. Here, we demonstrate a strategy for designing active materials for rechargeable aluminium batteries. This strategy entails the use of redox-active triangular phenanthrenequinone-based macrocycles, which form layered superstructures resulting in the reversible insertion and extraction of a cationic aluminium complex. This architecture exhibits an outstanding electrochemical performance with a reversible capacity of 110 mA h g–1 along with a superior cyclability of up to 5,000 cycles. Furthermore, electrodes composed of these macrocycles blended with graphite flakes result in higher specific capacity, electronic conductivity and areal loading. These findings constitute a major advance in the design of rechargeable aluminium batteries and represent a good starting point for addressing affordable large-scale energy storage.

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Fig. 1: Series of PQ derivatives for rechargeable ALBs.
Fig. 2: Electrochemical measurements of PQ derivatives.
Fig. 3: Ex situ characterization of PQ-Δ.
Fig. 4: Fabrication of the graphite-flake-blended PQ triangle hybrid (PQ-Δ-HY) and its electrochemical performance.
Fig. 5: Mechanical stability and electrochemical performance of the hybrid electrode.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.


  1. 1.

    Huggins, R. Advanced Batteries: Materials Science Aspects (Springer, 2008).

  2. 2.

    Dunn, B., Kamath, H. & Tarascon, J.-M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).

    Article  Google Scholar 

  3. 3.

    Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).

    Article  Google Scholar 

  4. 4.

    Tarascon, J.-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  Google Scholar 

  5. 5.

    Goodenough, J. B. & Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).

    Article  Google Scholar 

  6. 6.

    Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

    Article  Google Scholar 

  7. 7.

    Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).

    Article  Google Scholar 

  8. 8.

    Elia, G. A. et al. An overview and future perspectives of aluminum batteries. Adv. Mater. 28, 7564–7579 (2016).

    Article  Google Scholar 

  9. 9.

    Li, Q. & Bjerrum, N. J. Aluminum as anode for energy storage and conversion: a review. J. Power Sources 110, 1–10 (2002).

    Article  Google Scholar 

  10. 10.

    Canepa, P. et al. Odyssey of multivalent cathode materials: open questions and future challenges. Chem. Rev. 117, 4287–4341 (2017).

    Article  Google Scholar 

  11. 11.

    Muldoon, J., Bucur, C. B. & Gregory, T. Quest for nonaqueous multivalent secondary batteries: magnesium and beyond. Chem. Rev. 114, 11683–11720 (2014).

    Article  Google Scholar 

  12. 12.

    Yoo, D.-J., Kim, J.-S., Shin, J., Kim, K. J. & Choi, J. W. Stable performance of aluminum metal battery by incorporating lithium ion chemistry. ChemElectroChem 4, 2345–2351 (2017).

    Article  Google Scholar 

  13. 13.

    Dagorne, S. & Atwood, D. A. Synthesis, characterization, and applications of group 13 cationic compounds. Chem. Rev. 108, 4037–4071 (2008).

    Article  Google Scholar 

  14. 14.

    Atwood, D. A. Cationic group 13 complexes. Coord. Chem. Rev. 176, 407–430 (1998).

    Article  Google Scholar 

  15. 15.

    Buchanan, R. M. & Pierpont, C. G. Tautomeric catecholate-semiquinone interconversion via metalligand electron-transfer—structural, spectral, and magnetic-properties of (3,5-di-tert-butylcatecholato)-(3,5-di-tert-butylsemiquinone)(bipyridyl)cobalt(III), a complex containing mixed-valence organic-ligands. J. Am. Chem. Soc. 102, 4951–4957 (1980).

    Article  Google Scholar 

  16. 16.

    Piskunov, A. V., Maleeva, A. V., Fukin, G. K., Baranov, E. V. & Kuznetsova, O. V. Quinone complexes of aluminum: synthesis and structures. Russ. J. Coord. Chem. 36, 161–169 (2010).

    Article  Google Scholar 

  17. 17.

    Connelly, N. G. & Geiger, W. E. Chemical redox agents for organometallic chemistry. Chem. Rev. 96, 877–910 (1996).

    Article  Google Scholar 

  18. 18.

    Klimov, E. S., Lobanov, A. V. & Abakumov, G. A. Electron-spin-resonance spectra of chelate complexes of 1,2-naphthoquinone and 9,10-phenanthrenequinone with halides of group-III elements. Russ. Chem. Bull. 30, 1664–1666 (1981).

    Article  Google Scholar 

  19. 19.

    Barker, P. E., Hudson, A. & Jackson, R. A. The reaction of aluminium trichloride with 9,10-phenanthrenequinone. J. Organomet. Chem. 208, C1–C2 (1981).

    Article  Google Scholar 

  20. 20.

    Aurbach, D. et al. Prototype systems for rechargeable magnesium batteries. Nature 407, 724–727 (2000).

    Article  Google Scholar 

  21. 21.

    Hudak, N. S. Chloroaluminate-doped conducting polymers as positive electrodes in rechargeable aluminum batteries. J. Phys. Chem. C 118, 5203–5215 (2014).

    Article  Google Scholar 

  22. 22.

    Jayaprakash, N., Das, S. K. & Archer, L. A. The rechargeable aluminum-ion battery. Chem. Commun. 47, 12610–12612 (2011).

    Article  Google Scholar 

  23. 23.

    Zhang, J. et al. Metal-free phenanthrenequinone cyclotrimer as an effective heterogeneous catalyst. J. Am. Chem. Soc. 131, 11296–11297 (2009).

    Article  Google Scholar 

  24. 24.

    Ohtsuka, Y., Yoshida, J. & Nokami, T., inventors; Panasonic Corporation, assignee. Phenanthrenequinone compound, electrode active material, and power storage device. US patent 12,530,382 (2008).

  25. 25.

    Tang, L. et al. Preparation, structure, and electrochemical properties of reduced graphene sheet films. Adv. Funct. Mater. 19, 2782–2789 (2009).

    Article  Google Scholar 

  26. 26.

    Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater. 6, 183–191 (2007).

    Article  Google Scholar 

  27. 27.

    Schwab, M. G. et al. Torands revisited: metal sequestration and self-assembly of cyclo-2,9-tris-1,10-phenanthroline hexaaza macrocycles. Chem. Eur. J. 21, 8426–8434 (2015).

    Article  Google Scholar 

  28. 28.

    Lin, M.-C. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015).

    Article  Google Scholar 

  29. 29.

    Wang, S. et al. Aluminum chloride-graphite batteries with flexible current collectors prepared from Earth-abundant elements. Adv. Sci. 5, 1700712 (2018).

    Article  Google Scholar 

  30. 30.

    Hassan, F. M. et al. Evidence of covalent synergy in silicon-sulfur-graphene yielding highly efficient and long-life lithium-ion batteries. Nat. Commun. 6, 8597 (2015).

    Article  Google Scholar 

  31. 31.

    Kaim, W. Radical-forming electron-transfer reactions involving main-group organometallics. Acc. Chem. Res. 18, 160–166 (1985).

    Article  Google Scholar 

  32. 32.

    Koten, G. V., Jastrzebski, J. T. B. H. & Vrieze, K. Stable 1,4-diaza-1,3-butadiene(α-diimine)-zinc and -aluminium radicals formed in single electron transfer reactions: their consequences for organic syntheses. J. Organomet. Chem. 250, 49–61 (1983).

    Article  Google Scholar 

  33. 33.

    Razuvaev, G. A., Abakumov, G. A., Klimov, E. S., Gladyshev, E. N. & Bayushkin, P. Y. Reactions of sterically hindered o-quinones with alkyl derivatives of group III elements. Russ. Chem. Bull. 26, 1034–1037 (1977).

    Article  Google Scholar 

  34. 34.

    Kravchyk, K. V., Wang, S., Piveteau, L. & Kovalenko, M. V. Efficient aluminum chloride–natural graphite battery. Chem. Mater. 29, 4484–4492 (2017).

    Article  Google Scholar 

  35. 35.

    Kim, D. J. et al. Redox-active macrocycles for organic rechargeable batteries. J. Am. Chem. Soc. 139, 6635–6643 (2017).

    Article  Google Scholar 

  36. 36.

    Armand, M. et al. Conjugated dicarboxylate anodes for Li-ion batteries. Nat. Mater. 8, 120–125 (2009).

    Article  Google Scholar 

  37. 37.

    Morita, Y. et al. Organic tailored batteries materials using stable open-shell molecules with degenerate frontier orbitals. Nat. Mater. 10, 947–951 (2011).

    Article  Google Scholar 

  38. 38.

    Lee, M. et al. Organic nanohybrids for fast and sustainable energy storage. Adv. Mater. 26, 2558–2565 (2014).

    Article  Google Scholar 

  39. 39.

    Liang, Y., Tao, Z. & Chen, J. Organic electrode materials for rechargeable lithium batteries. Adv. Energy Mater. 2, 742–769 (2012).

    Article  Google Scholar 

  40. 40.

    Zhang, Z., Yoshikawa, H. & Awaga, K. Discovery of a “bipolar charging” mechanism in the solid-state electrochemical process of a flexible metal–organic framework. Chem. Mater. 28, 1298–1303 (2016).

    Article  Google Scholar 

  41. 41.

    Fang, C. et al. A metal–organic compound as cathode material with superhigh capacity achieved by reversible cationic and anionic redox chemistry for high‐energy sodium‐ion batteries. Angew. Chem. Int. Ed. 129, 6897–6901 (2017).

    Article  Google Scholar 

  42. 42.

    Wang, D.-Y. et al. Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode. Nat. Commun. 8, 14283 (2017).

    Article  Google Scholar 

  43. 43.

    Chen, C. J. et al. Highly conductive, lightweight, low-tortuosity carbon frameworks as ultrathick 3D current collectors. Adv. Energy Mater. 7, 1700595 (2017).

    Article  Google Scholar 

  44. 44.

    Lee, J. H. et al. Restacking-inhibited 3D reduced graphene oxide for high performance supercapacitor electrodes. ACS Nano 7, 9366–9374 (2013).

    Article  Google Scholar 

  45. 45.

    Wu, K. H., Wang, D. W. & Gentle, I. R. The value of mixed conduction for oxygen electroreduction on graphene-chitosan composites. Carbon 73, 234–243 (2014).

    Article  Google Scholar 

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This research was conducted as part of the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors acknowledge both KACST and NU for their financial support of this research. The Integrated Molecular Structure Education and Research Center (IMSERC) at NU is acknowledged for the use of its facilities. J.W.C. acknowledges support by National Research Foundation of Korea (NRF) grants funded by the Korea government (MEST) (NRF-2018R1A2A1A19023146, NRF-2017M1A2A2044477 and NRF-2018M1A2A2063340) and the Energy Efficiency and Resources Core Technology Programme of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), which is granted financial resources from the Ministry of Trade, Industry and Energy, Republic of Korea (20152020104870).

Author information




D.J.K. and D.-J.Y. designed and performed experimental work. D.J.K., M.T.O., A.P. and M.O. worked on synthesis and characterisation of active materials. D.-J.Y. measured ALB performance. D.-J.Y. and S.J.L. conducted ex-situ analysis of active materials. D.J.K., A.P., D.-J.Y., J.W.C. and J.F.S. wrote the manuscript. J.W.C. and J.F.S. directed this work. All authors discussed the results and commented on the manuscript.

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Correspondence to Jang Wook Choi or J. Fraser Stoddart.

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Supplementary Figures 1–21, Supplementary Note, Supplementary References

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Kim, D.J., Yoo, D., Otley, M.T. et al. Rechargeable aluminium organic batteries. Nat Energy 4, 51–59 (2019).

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