Abstract

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  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).

  3. 3.

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

  4. 4.

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

  5. 5.

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

  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).

  7. 7.

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

  8. 8.

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

  9. 9.

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

  10. 10.

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

  11. 11.

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

  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).

  13. 13.

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

  14. 14.

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

  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).

  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).

  17. 17.

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

  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).

  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).

  20. 20.

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

  21. 21.

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

  22. 22.

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

  23. 23.

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

  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).

  26. 26.

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

  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).

  28. 28.

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

  29. 29.

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

  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).

  31. 31.

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

  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).

  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).

  34. 34.

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

  35. 35.

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

  36. 36.

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

  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).

  38. 38.

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

  39. 39.

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

  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).

  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).

  42. 42.

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

  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).

  44. 44.

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

  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).

Download references

Acknowledgements

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

Author notes

    • Dong Jun Kim

    Present address: School of Chemistry, University of New South Wales, Sydney, New South Wales, Australia

  1. These authors contributed equally: Dong Jun Kim, Dong-Joo Yoo.

Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, IL, USA

    • Dong Jun Kim
    • , Michael T. Otley
    • , Cristian Pezzato
    • , Magdalena Owczarek
    •  & J. Fraser Stoddart
  2. School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    • Dong-Joo Yoo
    •  & Jang Wook Choi
  3. Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL, USA

    • Aleksandrs Prokofjevs
  4. Graduate School of Energy, Environment, Water, and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea

    • Seung Jong Lee
  5. Institute for Molecular Design and Synthesis, Tianjin University, Tianjin, P. R. China

    • J. Fraser Stoddart

Authors

  1. Search for Dong Jun Kim in:

  2. Search for Dong-Joo Yoo in:

  3. Search for Michael T. Otley in:

  4. Search for Aleksandrs Prokofjevs in:

  5. Search for Cristian Pezzato in:

  6. Search for Magdalena Owczarek in:

  7. Search for Seung Jong Lee in:

  8. Search for Jang Wook Choi in:

  9. Search for J. Fraser Stoddart in:

Contributions

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.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Jang Wook Choi or J. Fraser Stoddart.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–21, Supplementary Note, Supplementary References

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41560-018-0291-0