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Organic tailored batteries materials using stable open-shell molecules with degenerate frontier orbitals

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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Figure 1: Chemical structures and energy diagrams for only the SOMO and LUMO(s) of 6-oxophenalenoxyl (6OPO) (left), tri-tert-butylated trioxotriangulene ((t-Bu)3TOT) (centre) and tribrominated trioxotriangulene (Br3TOT) (right).
Figure 2: Redox behaviours of (t-Bu)3TOT and Br3TOT in solution.
Figure 3: Charge–discharge curves and cycle performances for 100 cycles of discharge processes on the coin-type cells.
Figure 4: Charge–discharge properties of the coin-type cells of Br3TOT.

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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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Correspondence to Yasushi Morita or Takeji Takui.

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The authors declare no competing financial interests.

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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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