P2-type Na(x)[Fe(1/2)Mn(1/2)]O2 made from earth-abundant elements for rechargeable Na batteries.

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 materials, such as LiMn(2)O(4) and LiFePO(4), 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 materials, 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-Na(2/3)[Fe(1/2)Mn(1/2)]O(2), that delivers 190 mAh g(-1) of reversible capacity in the sodium cells with the electrochemically active Fe(3+)/Fe(4+) redox. These results will contribute to the development of rechargeable batteries from the earth-abundant elements operable at room temperature.

[1]  M. Deem,et al.  A general recursion method for calculating diffracted intensities from crystals containing planar faults , 1991, Proceedings of the Royal Society of London. Series A: Mathematical and Physical Sciences.

[2]  Tsutomu Ohzuku,et al.  Electrochemistry of manganese dioxide in lithium nonaqueous cell. I: X-ray diffractional study on the reduction of electrolytic manganese dioxide , 1990 .

[3]  G. H. Newman,et al.  Ambient Temperature Cycling of an Na ‐ TiS2 Cell , 1980 .

[4]  Tsutomu Ohzuku,et al.  Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell , 1990 .

[5]  F. Izumi,et al.  Three-Dimensional Visualization in Powder Diffraction , 2007 .

[6]  Anton Van der Ven,et al.  First-principles investigation of phase stability in Li x CoO 2 , 1998 .

[7]  P. Hagenmuller,et al.  Electrochemical intercalation of sodium in NaxCoO2 bronzes , 1981 .

[8]  Zhonghua Lu,et al.  In Situ X-Ray Diffraction Study of P 2 ­ Na2 / 3 [ Ni1 / 3Mn2 / 3 ] O 2 , 2001 .

[9]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[10]  Zhonghua Lu,et al.  Staging Phase Transitions in Li x CoO2 , 2002 .

[11]  Luis Sánchez,et al.  Synthesis and characterization of high-temperature hexagonal P2-Na0.6 MnO2 and its electrochemical behaviour as cathode in sodium cells , 2002 .

[12]  M Newville,et al.  IFEFFIT: interactive XAFS analysis and FEFF fitting. , 2001, Journal of synchrotron radiation.

[13]  Donghan Kim,et al.  Enabling Sodium Batteries Using Lithium‐Substituted Sodium Layered Transition Metal Oxide Cathodes , 2011 .

[14]  Wataru Murata,et al.  Fluorinated ethylene carbonate as electrolyte additive for rechargeable Na batteries. , 2011, ACS applied materials & interfaces.

[15]  J. Tarascon,et al.  Na2Ti3O7: Lowest Voltage Ever Reported Oxide Insertion Electrode for Sodium Ion Batteries. , 2011 .

[16]  Y. Takeda,et al.  Preparation of LiFeO2 with Alpha‐ NaFeO2‐Type Structure Using a Mixed‐Alkaline Hydrothermal Method , 1997 .

[17]  S. Okada,et al.  Layered Transition Metal Oxides as Cathodes for Sodium Secondary Battery , 2006 .

[18]  Shinichi Komaba,et al.  Electrochemical intercalation activity of layered NaCrO2 vs. LiCrO2 , 2010 .

[19]  Gerbrand Ceder,et al.  First-principles investigation of phase stability in Li x CoO 2 , 1998 .

[20]  P. Hagenmuller,et al.  Structural classification and properties of the layered oxides , 1980 .

[21]  Kazuma Gotoh,et al.  Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard‐Carbon Electrodes and Application to Na‐Ion Batteries , 2011 .

[22]  C. Delmas,et al.  Electrochemical Na-Deintercalation from NaVO2 , 2011 .

[23]  J. Rehr,et al.  Theoretical approaches to x-ray absorption fine structure , 2000 .

[24]  K. Kubota,et al.  Structure and electrode reactions of layered rocksalt LiFeO 2 nanoparticles for lithium battery cath , 2011 .

[25]  Y. Koyama,et al.  First Principles Study on Factors Determining Battery Voltages of LiMO2 (M=Ti-Ni) , 1999 .

[26]  Jean-Marie Tarascon,et al.  Na2Ti3O7: Lowest voltage ever reported oxide insertion electrode for sodium ion batteries , 2011 .

[27]  C. Delmas,et al.  Non-cooperative Jahn-Teller effect in LiNiO2: An EXAFS study , 1995 .

[28]  K. Abraham Intercalation positive electrodes for rechargeable sodium cells , 1982 .

[29]  M. Stanley Whittingham,et al.  Chemistry of intercalation compounds: Metal guests in chalcogenide hosts , 1978 .

[30]  Fujio Izumi,et al.  VESTA: a three-dimensional visualization system for electronic and structural analysis , 2008 .

[31]  Yasuo Takeda,et al.  Sodium deintercalation from sodium iron oxide , 1994 .

[32]  D Carlier,et al.  Electrochemical investigation of the P2–NaxCoO2 phase diagram. , 2011, Nature materials.