Better cycling performances of bulk Sb in Na-ion batteries compared to Li-ion systems: an unexpected electrochemical mechanism.

Pure micrometric antimony can be successfully used as negative electrode material in Na-ion batteries, sustaining a capacity close to 600 mAh g(-1) at a high rate with a Coulombic efficiency of 99 over 160 cycles, an extremely high capacity compared to any other compound tested against both Li and Na. The reaction mechanism with Na does not simply go through the alloying mechanism observed for Li where the intermediate species are those expected from the phase diagram. In the case of Na, the intermediate phases are mostly amorphous and could not be precisely identified. Surprisingly, we evidenced that a competition takes place at the end of the discharge of the Sb/Na cell between the formation of the hexagonal and the cubic polymorphs of Na(3)Sb, the last being described in the literature as unstable at atmospheric pressure and only synthesized under high pressure (1-9 GPa). In addition, fluoroethylene carbonate added to the electrolyte combined with an appropriate electrode formulation based on carboxymethyl cellulose, carbon black, and vapor ground carbon fibers seems to be determinant in the excellent performances of this material.

[1]  Ricardo Alcántara,et al.  Carbon Microspheres Obtained from Resorcinol-Formaldehyde as High-Capacity Electrodes for Sodium-Ion Batteries , 2005 .

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

[3]  B. Lestriez,et al.  Significant electrochemical performance improvement of TiSnSb as anode material for Li-ion batteries with composite electrode formulation and the use of VC and FEC electrolyte additives , 2012 .

[4]  Adam Heller,et al.  High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries. , 2012, Chemical communications.

[5]  R. Huggins,et al.  Thermodynamic Properties of the Intermetallic Systems Lithium‐Antimony and Lithium‐Bismuth , 1978 .

[6]  C. Villevieille,et al.  A new ternary Li4FeSb2 structure formed upon discharge of the FeSb2/Li cell , 2009 .

[7]  J. Dahn,et al.  Electrochemistry of InSb as a Li Insertion Host: Problems and Prospects , 2001 .

[8]  John T. Vaughey,et al.  Phase transitions in lithiated Cu2Sb anodes for lithium batteries: an in situ X-ray diffraction study , 2001 .

[9]  Wei Wang,et al.  High capacity, reversible alloying reactions in SnSb/C nanocomposites for Na-ion battery applications. , 2012, Chemical communications.

[10]  R. Huggins,et al.  Behavior of Some Binary Lithium Alloys as Negative Electrodes in Organic Solvent‐Based Electrolytes , 1986 .

[11]  Mark N. Obrovac,et al.  Reversible Insertion of Sodium in Tin , 2012 .

[12]  S. Kulinich,et al.  High-Pressure Phase Transition of Hexagonal Alkali Pnictides , 2003 .

[13]  Xinping Ai,et al.  High capacity Na-storage and superior cyclability of nanocomposite Sb/C anode for Na-ion batteries. , 2012, Chemical communications.

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

[15]  Anubhav Jain,et al.  Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials , 2011 .

[16]  P. Moreau,et al.  Hierarchical and Resilient Conductive Network of Bridged Carbon Nanotubes and Nanofibers for High-Energy Si Negative Electrodes , 2009 .

[17]  K. Edström,et al.  Influence of electrode microstructure on the reactivity of Cu2Sb with lithium , 2007 .

[18]  Shinichi Komaba,et al.  Electrochemically Reversible Sodium Intercalation of Layered NaNi0.5Mn0.5O2 and NaCrO2 , 2009 .

[19]  A. Pelton,et al.  The Na-Sb (sodium-antimony) system , 1993 .

[20]  Marca M. Doeff,et al.  Electrochemical Insertion of Sodium into Carbon , 1993 .

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

[22]  Jean-Marie Tarascon,et al.  Is lithium the new gold? , 2010, Nature chemistry.

[23]  Gerbrand Ceder,et al.  Electrode Materials for Rechargeable Sodium‐Ion Batteries: Potential Alternatives to Current Lithium‐Ion Batteries , 2012 .

[24]  NiSb2 as negative electrode for Li-ion batteries: An original conversion reaction , 2007 .

[25]  P. Soudan,et al.  Improvement of intermetallics electrochemical behavior by playing with the composite electrode formulation , 2011 .

[26]  Pedro Lavela,et al.  NiCo2O4 Spinel: First Report on a Transition Metal Oxide for the Negative Electrode of Sodium-Ion Batteries , 2002 .

[27]  Zhenguo Yang,et al.  Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life , 2011, Advanced materials.

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

[29]  J. Cabana,et al.  Beyond Intercalation‐Based Li‐Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions , 2010, Advanced materials.

[30]  Gregory A. Roberts,et al.  Effect of fluoroethylene carbonate (FEC) on the performance and surface chemistry of Si-nanowire Li-ion battery anodes. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[31]  Stéphanie Belin,et al.  An Electrochemical Cell for Operando Study of Lithium Batteries Using Synchrotron Radiation , 2010 .