A comprehensive study on the cell chemistry of the sodium superoxide (NaO2) battery.

This work reports on the cell chemistry of a room temperature sodium-oxygen battery using an electrolyte of diethylene glycol dimethyl ether (diglyme) and sodium trifluoromethanesulfonate (NaSO3CF3, sodium triflate). Different from lithium-oxygen cells, where lithium peroxide is found as the discharge product, sodium superoxide (NaO2) is formed in the present cell, with overpotentials as low as 100 mV during charging. Several analytical methods are used to follow the cell reaction during discharge and charge. Changes in structure and morphology are studied by SEM and XRD. It is found that NaO2 grows as cubic particles with feed sizes in the range of 10-50 μm; upon recharge the particles consecutively decompose. Pressure monitoring during galvanostatic cycling shows that the coulombic efficiency (e(-)/O2) for discharge and charge is approx. 1.0, the expected value for NaO2 formation. Also optical spectroscopy is identified as a convenient and useful tool to follow the discharge-charge process. The maximum discharge capacity is found to be limited by oxygen transport within the electrolyte soaked carbon fiber cathode and pore blocking near the oxygen interface is observed. Finally electrolyte decomposition and sodium dendrite growth are identified as possible reasons for the limited capacity retention of the cell. The occurrence of undesired side reactions is analyzed by DEMS measurements during cycling as well as by post mortem XPS investigations.

[1]  Stefan A Freunberger,et al.  The carbon electrode in nonaqueous Li-O2 cells. , 2013, Journal of the American Chemical Society.

[2]  D. H. Templeton,et al.  POLYMORPHISM OF SODIUM SUPEROXIDE , 1953 .

[3]  J. A. Taylor,et al.  Contributions to screening in the solid state by electron systems of remote atoms: Effects to photoelectron and Auger transitions , 1982 .

[4]  N. Dudney,et al.  Influence of Lithium Salts on the Discharge Chemistry of Li-Air Cells. , 2012, The journal of physical chemistry letters.

[5]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[6]  Qian Sun,et al.  An enhanced electrochemical performance of a sodium-air battery with graphene nanosheets as air electrode catalysts. , 2013, Chemical communications.

[7]  Yuhui Chen,et al.  The lithium-oxygen battery with ether-based electrolytes. , 2011, Angewandte Chemie.

[8]  Hubert A. Gasteiger,et al.  Using Rotating Ring Disc Electrode Voltammetry to Quantify the Superoxide Radical Stability of Aprotic Li–Air Battery Electrolytes , 2012 .

[9]  Jasim Uddin,et al.  A rechargeable Li-O2 battery using a lithium nitrate/N,N-dimethylacetamide electrolyte. , 2013, Journal of the American Chemical Society.

[10]  Michel Armand,et al.  A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries , 2013, Nature Communications.

[11]  D. O’Sullivan,et al.  The kinetics of complex formation between Ti(IV) and hydrogen peroxide , 2007 .

[12]  A. L. Patterson.  The Scherrer Formula for X-Ray Particle Size Determination , 1939 .

[13]  V. Nefedov,et al.  A comparison of different spectrometers and charge corrections used in X-ray photoelectron spectroscopy , 1977 .

[14]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[15]  Yiying Wu,et al.  A low-overpotential potassium-oxygen battery based on potassium superoxide. , 2013, Journal of the American Chemical Society.

[16]  G. Eisenberg.  Colorimetric Determination of Hydrogen Peroxide , 1943 .

[17]  R M Shelby,et al.  Solvents' Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry. , 2011, The journal of physical chemistry letters.

[18]  Doron Aurbach,et al.  The electrochemistry of noble metal electrodes in aprotic organic solvents containing lithium salts , 1991 .

[19]  Shao Hua Yang,et al.  Design and analysis of aluminum/air battery system for electric vehicles , 2002 .

[20]  Wu Xu,et al.  Optimization of Air Electrode for Li/Air Batteries , 2010 .

[21]  Gil Cohn,et al.  Study and development of non-aqueous silicon-air battery , 2010 .

[22]  Qian Sun,et al.  Electrochemical properties of room temperature sodium-air batteries with non-aqueous electrolyte , 2012 .

[23]  Matthew H. Ervin,et al.  Oxygen Transport Properties of Organic Electrolytes and Performance of Lithium/Oxygen Battery , 2003 .

[24]  H. Wriedt.  The Na−O (Sodium-Oxygen) System , 1987 .

[25]  Sun Tai Kim,et al.  Metal–Air Batteries with High Energy Density: Li–Air versus Zn–Air , 2010 .

[26]  P. Bruce,et al.  Rechargeable LI2O2 electrode for lithium batteries. , 2006, Journal of the American Chemical Society.

[27]  Yang Shao-Horn,et al.  The discharge rate capability of rechargeable Li–O2 batteries , 2011 .

[28]  Philipp Adelhelm,et al.  A rechargeable room-temperature sodium superoxide (NaO2) battery. , 2013, Nature materials.

[29]  Donald J. Siegel,et al.  Lithium peroxide surfaces are metallic, while lithium oxide surfaces are not. , 2012, Journal of the American Chemical Society.

[30]  Won Il Cho,et al.  Electrochemical Performances of Lithium-air Cell with Carbon Materials , 2010 .

[31]  Dan Zhao,et al.  Microfocused X-ray study on precipitate formation in the separator region of nonaqueous Li-O(2) batteries. , 2012, ChemSusChem.

[32]  Ji‐Guang Zhang,et al.  The stability of organic solvents and carbon electrode in nonaqueous Li-O2 batteries , 2012 .

[33]  J. Nørskov,et al.  Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li-O2 Batteries. , 2012, The journal of physical chemistry letters.

[34]  Linda F. Nazar,et al.  Screening for superoxide reactivity in Li-O2 batteries: effect on Li2O2/LiOH crystallization. , 2012, Journal of the American Chemical Society.

[35]  B. Grzybowski,et al.  Charged nanoparticles as supramolecular surfactants for controlling the growth and stability of microcrystals. , 2012, Nature materials.

[36]  Vanchiappan Aravindan,et al.  Lithium-ion conducting electrolyte salts for lithium batteries. , 2011, Chemistry.

[37]  T. Ishihara,et al.  High capacity of an Fe-air rechargeable battery using LaGaO3-based oxide ion conductor as an electrolyte. , 2012, Physical chemistry chemical physics : PCCP.

[38]  T. Shiga,et al.  Cathode reaction mechanism of non-aqueous Li–O2 batteries with highly oxygen radical stable electrolyte solvent , 2013 .