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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Ohzuku, T., Kitagawa, M. & Hirai, T. Electrochemistry of manganese-dioxide in lithium nonaqueous cell. 3. X-ray diffractional study on the reduction of spinel-related manganese-dioxide. J. Electrochem. Soc. 137, 769–775 (1990).
Padhi, A. K., Nanjundaswamy, K. S. & Goodenough, J. B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).
Okada, S. et al. Layered transition metal oxides as cathodes for sodium secondary battery. ECS Meeting Abstr. 602, 201 (2006).
Kim, D. et al. Enabling sodium batteries using lithium-substituted sodium layered transition metal oxide cathodes. Adv. Energy Mater. 1, 333–336 (2011).
Komaba, S., Takei, C., Nakayama, T., Ogata, A. & Yabuuchi, N. Electrochemical intercalation activity of layered NaCrO2 vs LiCrO2 . Electrochem. Commun. 12, 355–358 (2010).
Komaba, S. et al. Electrochemical Na insertion and solid electrolyte interphase for hard-carbon electrodes and application to Na-ion batteries. Adv. Funct. Mater. 21, 3859–3867 (2011).
Newman, G. H. & Klemann, L. P. Ambient-temperature cycling of an Na-TiS2 cell. J. Electrochem. Soc. 127, 2097–2099 (1980).
Whittingham, M. S. Chemistry of intercalation compounds—metal guests in chalcogenide hosts. Prog. Solid State Chem. 12, 41–99 (1978).
Abraham, K. M. Intercalation positive electrodes for rechargeable sodium cells. Solid State Ion. 7, 199–212 (1982).
Delmas, C., Fouassier, C. & Hagenmuller, P. Structural classification and properties of the layered oxides. Physica B+C 99, 81–85 (1980).
Delmas, C., Braconnier, J. J., Fouassier, C. & Hagenmuller, P. Electrochemical intercalation of sodium in NaxCoO2 bronzes. Solid State Ion. 3–4, 165–169 (1981).
Didier, C. et al. Electrochemical Na-deintercalation from NaVO2 . Electrochem. Solid-State Lett. 14, A75–A78 (2011).
Caballero, A. et al. Synthesis and characterization of high-temperature hexagonal P2-Na0.6MnO2 and its electrochemical behaviour as cathode in sodium cells. J. Mater. Chem. 12, 1142–1147 (2002).
Berthelot, R., Carlier, D. & Delmas, C. Electrochemical investigation of the P2-NaxCoO2 phase diagram. Nature Mater. 10, 74–80 (2011).
Lu, Z. & Dahn, J. R. In situ X-ray diffraction study of P2-Na2/3[Ni1/3Mn2/3]O2 . J. Electrochem. Soc. 148, A1225–A1229 (2001).
Treacy, M. M. J., Newsam, J. M. & Deem, M. W. A general recursion method for calculating diffracted intensities from crystals containing planar faults. Proc. R. Soc. Lond. Ser. A 433, 499–520 (1991).
Van der Ven, A., Aydinol, M. K., Ceder, G., Kresse, G. & Hafner, J. First-principles investigation of phase stability in LixCoO2 . Phys. Rev. B 58, 2975–2987 (1998).
Chen, Z. H., Lu, Z. H. & Dahn, J. R. Staging phase transitions in LixCoO2 . J. Electrochem. Soc. 149, A1604–A1609 (2002).
Rougier, A., Delmas, C. & Chadwick, A. V. Noncooperative Jahn–Teller effect in LiNiO2—an EXAFS study. Solid State Commun. 94, 123–127 (1995).
Takeda, Y. et al. Sodium deintercalation from sodium iron-oxide. Mater. Res. Bull. 29, 659–666 (1994).
Ado, K. et al. Preparation of LiFeO2 with α-NaFeO2-type structure using a mixed-alkaline hydrothermal method. J. Electrochem. Soc. 144, L177–L180 (1997).
Hirayama, M., Tomita, H., Kubota, K. & Kanno, R. Structure and electrode reactions of layered rocksalt LiFeO2 nanoparticles for lithium battery cathode. J. Power Sources 196, 6809–6814 (2011).
Koyama, Y., Tanaka, I., Kim, Y. S., Nishitani, S. R. & Adachi, H. First principles study on factors determining battery voltages of LiMO2 (M = Ti–Ni). Jpn. J. Appl. Phys. 38, 4804–4808 (1999).
Senguttuvan, P., Rousse, G. l., Seznec, V., Tarascon, J-M. & Palacín, M. R. Na2Ti3O7: Lowest voltage ever reported oxide insertion electrode for sodium ion batteries. Chem. Mater. 23, 4109–4111 (2011).
Komaba, S. et al. Fluorinated ethylene carbonate as electrolyte additive for rechargeable Na batteries. ACS Appl. Mater. Interf. 3, 4165–4168 (2011).
Nishibori, E. et al. The large Debye–Scherrer camera installed at SPring-8 BL02B2 for charge density studies. Nucl. Instrum. Meth. 467, 1045–1048 (2001).
Izumi, F. & Momma, K. Three-dimensional visualization in powder diffraction. Solid State Phenom. 130, 15–20 (2007).
Momma, K. & Izumi, F. VESTA: A three-dimensional visualization system for electronic and structural analysis. J. Appl. Crystallogr. 41, 653–658 (2008).
Newville, M. IFEFFIT: Interactive XAFS analysis and FEFF fitting. J. Synchrot. Radiat. 8, 322–324 (2001).
Rehr, J. J. & Albers, R. C. Theoretical approaches to X-ray absorption fine structure. Rev. Mod. Phys. 72, 621–654 (2000).
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).
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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