P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries

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Abstract

Rechargeable lithium batteries have risen to prominence as key devices for green and sustainable energy development. Electric vehicles, which are not equipped with an internal combustion engine, have been launched in the market. Manganese- and iron-based positive-electrode materials1,2, such as LiMn2O4 and LiFePO4, are used in large-scale batteries for electric vehicles. Manganese and iron are abundant elements in the Earth’s crust, but lithium is not. In contrast to lithium, sodium is an attractive charge carrier on the basis of elemental abundance. Recently, some layered materials3,4,5,6, where sodium can be electrochemically and reversibly extracted/inserted, have been reported. However, their reversible capacity is typically limited to 100 mAh g−1. Herein, we report a new electrode material, P2-Na2/3[Fe1/2Mn1/2]O2, that delivers 190 mAh g−1 of reversible capacity in the sodium cells with the electrochemically active Fe3+/Fe4+ redox. These results will contribute to the development of rechargeable batteries from the earth-abundant elements operable at room temperature.

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Figure 1: Structural characterization of P2-type and O3-type crystal structures.
Figure 2: Electrode performance.
Figure 3: Characterization of P2-type Nax[Fe1/2Mn1/2]O2 by SXRD, XAS and Mössbauer spectroscopy.
Figure 4: A comparison of reversible capacity and operating voltage ranges of the layered sodium insertion materials1,2,3,4,5,6,11,12,13,14,15.

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Acknowledgements

This study was partly supported by the NEXT programme of the JSPS. The SXRD experiments were made possible through the support of the Japanese Ministry of Education, Science, Sports and Culture, Nanotechnology Support Project (Proposal No. 2010A1656 and 2011A1650) with the approval of the Japan Synchrotron Radiation Research Institute (JASRI). The synchrotron X-ray absorption work was done under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2010G156 and 2011G141).

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N.Y. and S.K. conceived and designed the experiments. N.Y., M.K. and S.K. wrote the manuscript. M.K., J.I. and N.Y. carried out the experiments and analysed data. R.U. and Y.Y. performed the Mössbauer measurements and analysed the data, and discussed the results. H.N., S.H. and R.O. participated in analysis and discussions of the results and in preparing the manuscript.

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Correspondence to Shinichi Komaba.

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The authors declare no competing financial interests.

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Yabuuchi, N., Kajiyama, M., Iwatate, J. et al. P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries. Nature Mater 11, 512–517 (2012). https://doi.org/10.1038/nmat3309

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