Abstract
Secondary batteries using organic electrode-active materials promise to surpass present Li-ion batteries in terms of safety and resource price1,2. The use of organic polymers for cathode-active materials has already achieved a high voltage and cycle performance comparable to those of Li-ion batteries3,4,5,6. It is therefore timely to develop approaches for high-capacity organic materials-based battery applications. Here we demonstrate organic tailored batteries with high capacity by using organic molecules with degenerate molecular orbitals (MOs) as electrode-active materials. Trioxotriangulene (TOT), an organic open-shell molecule, with a singly occupied MO (SOMO) and two degenerate lowest-unoccupied MOs (LUMOs) was investigated. A tri-tert-butylated derivative ((t-Bu)3TOT)exhibited a high discharge capacity of more than 300 A h kg−1, exceeding those delivered by Li-ion batteries. A tribrominated derivative (Br3TOT) was also shown to increase the output voltage and cycle performance up to 85% after 100 cycles of the charge–discharge processes.
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References
Tarascon, J-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Armand, M. & Tarascon, J-M. Building better batteries. Nature 451, 652–657 (2008).
Nakahara, K. et al. Rechargeable batteries with organic radical cathodes. Chem. Phys. Lett. 359, 351–354 (2002).
Nishide, H. et al. Organic radical battery: Nitroxide polymers as a cathode-active material. Electrochim. Acta 50, 827–831 (2004).
Qu, J. et al. Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxyl radicals. Chem. Eur. J. 13, 7965–7973 (2007).
Nishide, H. & Oyaizu, K. Toward flexible batteries. Science 319, 737–738 (2008).
Herle, P. S., Ellis, B., Coombs, N. & Nazar, L. F. Nano-network electronic conduction in iron and nickel olivine phosphates. Nature Mater. 3, 147–152 (2004).
Aricò, A. S., Bruce, P., Scrosati, B., Tarascon, J. M. & van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nature Mater. 4, 366–377 (2005).
Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).
Ozawa, K. (ed.) in Lithium Ion Rechargeable Batteries (Wiley-VCH, 2009).
Nam, K. T. et al. Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes. Science 312, 885–888 (2006).
Sun, Y-K. et al. High-energy cathode material for long-life and safe lithium batteries. Nature Mater. 8, 320–324 (2009).
Goodenough, J. B. & Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 22, 587–603 (2010).
Ellis, B. L., Lee, K. T. & Nazar, L. F. Positive electrode materials for Li-ion and Li-batteries. Chem. Mater. 22, 691–714 (2010).
Armand, M. et al. Conjugated dicarboxylate anodes for Li-ion batteries. Nature Mater. 8, 120–125 (2009).
Walker, W. et al. Ethoxycarbonyl-based organic electrode for Li-batteries. J. Am. Chem. Soc. 132, 6517–6523 (2010).
Nguyen, T. L. A. et al. 3-D coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: Synthesis, characterization, and oxidation issues. Inorg. Chem. 49, 7135–7143 (2010).
Morita, Y. et al. A new trend in phenalenyl chemistry: A persistent neutral radical, 2,5,8-tri-tert-butyl-1,3-diazaphenalenyl, and the excited triplet state of the gable syn-dimer in the crystal of column motif. Angew. Chem. Int. Ed. 41, 1793–1796 (2002).
Morita, Y. et al. Redox-based spin diversity in a 6-oxophenalenoxyl system: Generation, ESR/ENDOR/TRIPLE, and theoretical studies of 2,5,8-tri-tert-butylphenalenyl-1,6-bis(olate) salts. Org. Lett. 4, 1985–1988 (2002).
Morita, Y., Okafuji, T. & Satoh, M. Molecular crystalline secondary batteries. Jpn. Kokai Tokkyo Koho, JP 2007227186 A (2007).
Morita, Y. & Nishida, S. in Stable Radicals: Fundamental and Applied Aspects of Odd-electron Compounds (ed. Hicks, R. G.) Ch. 3 (Wiley, 2010).
Morita, Y., Suzuki, S., Sato, K. & Takui, T. Synthetic organic spin chemistry for structurally well-defined open-shell graphene fragments. Nature Chem. 3, 197–204 (2011).
Morita, Y. et al. New persistent radicals: Synthesis and electronic spin structure of 2,5-di-tert-butyl-6-oxophenalenoxyl derivatives. J. Am. Chem. Soc. 122, 4825–4826 (2000).
Morita, Y., Nishida, S., Kawai, J., Takui, T. & Nakasuji, K Oxophenalenoxyl: Novel stable neutral radicals with a unique spin-delocalized nature depending on topological symmetries and redox states. Pure Appl. Chem. 80, 507–517 (2008).
Yoshikawa, H., Kazama, C., Awaga, K., Satoh, M. & Wada, J. Rechargeable molecular cluster batteries. Chem. Commun. 3169–3170 (2007).
Scrosati, B. Charging towards the superbattery. Nature 473, 448–449 (2011).
Acknowledgements
We thank K. Senoo and Y. Sasaki, JEOL, for their technical assistance. We also thank R. Tsuji, KANEKA Corporation, for his technical advice. This work was supported by the Yazaki Memorial Foundation for Science and Technology, the Japan Securities Scholarship Foundation, the CASIO Science Promotion Foundation, the Iwatani Naoji Foundation, the Canon Foundation, Grants-in-Aid for Scientific Research on Innovative Areas (No. 20110006 and Quantum Cybernetics) and Elements Science and Technology Project from the Ministry of Education, Culture, Sports, Science and Technology, Japan, also by the Funding Program for World-Leading R&D on Science and Technology (FIRST-JSPS, ‘Quantum Information Processes’) and CREST-JST, ‘Implementation of Quantum Computers/Quantum Information Processing Systems’.
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Y.M., S.N. and T.T. planned this project and carried out the experimental and theoretical work. M.S. and K.A. fabricated the coin-type cells and performed the charge–discharge experiments. T.M., M.M. and A.U. took part in the synthesis work for the molecules. K.S. carried out theoretical calculations.
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Morita, Y., Nishida, S., Murata, T. et al. Organic tailored batteries materials using stable open-shell molecules with degenerate frontier orbitals. Nature Mater 10, 947–951 (2011). https://doi.org/10.1038/nmat3142
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DOI: https://doi.org/10.1038/nmat3142
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