Aprotic Li–O2 Battery: Influence of Complexing Agents on Oxygen Reduction in an Aprotic Solvent

Several problems arise at the O2 (positive) electrode in the Li-air battery, including solvent/electrode decomposition and electrode passivation by insulating Li2O2. Progress partially depends on exploring the basic electrochemistry of O2 reduction. Here we describe the effect of complexing-cations on the electrochemical reduction of O2 in DMSO in the presence and absence of a Li salt. The solubility of alkaline peroxides in DMSO is enhanced by the complexing-cations, consistent with their strong interaction with reduced O2. The complexing-cations also increase the rate of the 1-electron O2 reduction to O2*- by up to six-fold (k° = 2.4 ×10-3 to 1.5 × 10-2 cm s-1) whether or not Li+ ions are present. In the absence of Li+, the complexing-cations also promote the reduction of O2*- to O22-. In the presence of Li+ and complexing-cations, and despite the interaction of the reduced O2 with the latter, SERS confirms that the product is still Li2O2.

[1]  Xiao‐Qing Yang,et al.  Catalytic disproportionation of the superoxide intermediate from electrochemical O2 reduction in nonaqueous electrolytes. , 2013, Chemistry.

[2]  E. Calvo,et al.  A rotating ring disk electrode study of the oxygen reduction reaction in lithium containing non aqueous electrolyte , 2013 .

[3]  Yuhui Chen,et al.  Charging a Li-O₂ battery using a redox mediator. , 2013, Nature chemistry.

[4]  H. S. Lee,et al.  Electrochemical oxidation of solid Li2O2 in non-aqueous electrolyte using peroxide complexing additives for lithium–air batteries , 2013 .

[5]  J. Nørskov,et al.  Li-O2 Kinetic Overpotentials: Tafel Plots from Experiment and First-Principles Theory. , 2013, The journal of physical chemistry letters.

[6]  E. Plichta,et al.  Oxygen Reduction Reactions in Ionic Liquids and the Formulation of a General ORR Mechanism for Li–Air Batteries , 2012 .

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

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

[9]  Y. Shao-horn,et al.  Reversible Reduction of Oxygen to Peroxide Facilitated by Molecular Recognition , 2012, Science.

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

[11]  Sanjeev Mukerjee,et al.  Rechargeable Lithium/TEGDME- LiPF6 ∕ O2 Battery , 2011 .

[12]  A. Gniewek,et al.  Structure, dynamics and catalytic activity of palladium(II) complexes with imidazole ligands , 2010 .

[13]  Sanjeev Mukerjee,et al.  Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery , 2010 .

[14]  Sylvie Grugeon,et al.  Boron esters as tunable anion carriers for non-aqueous batteries electrochemistry. , 2010, Journal of the American Chemical Society.

[15]  Wu Xu,et al.  Effects of Nonaqueous Electrolytes on the Performance of Lithium/Air Batteries , 2010 .

[16]  Xuejie Huang,et al.  A pentafluorophenylboron oxalate additive in non-aqueous electrolytes for lithium batteries , 2009 .

[17]  Sanjeev Mukerjee,et al.  Elucidating the Mechanism of Oxygen Reduction for Lithium-Air Battery Applications , 2009 .

[18]  C. Lagrost,et al.  Diffusion of molecules in ionic liquids/organic solvent mixtures. Example of the reversible reduction of O2 to superoxide. , 2009, The journal of physical chemistry. B.

[19]  R. Compton,et al.  Unusual Voltammetry of the Reduction of O2 in [C4dmim][N(Tf)2] Reveals a Strong Interaction of O2•− with the [C4dmim]+ Cation , 2008 .

[20]  James McBreen,et al.  New electrolytes using Li2O or Li2O2 oxides and tris(pentafluorophenyl) borane as boron based anion receptor for lithium batteries , 2008 .

[21]  R. G. Evans,et al.  Electroreduction of Oxygen in a Series of Room Temperature Ionic Liquids Composed of Group 15-Centered Cations and Anions , 2004 .

[22]  Keli Han,et al.  Photodissociation of solvated metal cation complexes Mg+(OCNC2H5)(n) (n=1-3) , 2004 .

[23]  J. Wadhawan,et al.  Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram re , 2003 .

[24]  R. Compton,et al.  Variable-Temperature Microelectrode Voltammetry: Application to Diffusion Coefficients and Electrode Reaction Mechanisms , 1999 .

[25]  J. Creighton,et al.  Resonance Raman scattering from the superoxide ion , 1998 .

[26]  K. M. Abraham,et al.  A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery , 1996 .

[27]  D. Lide Handbook of Chemistry and Physics , 1992 .

[28]  M. J. Weaver,et al.  Surface-enhanced Raman scattering at gold electrodes: dependence on electrochemical pretreatment conditions and comparisons with silver , 1987 .

[29]  Surjit Singh,et al.  Raman spectral studies of solutions of alkali metal perchlorates in dimethyl sulfoxide and water , 1985 .

[30]  L. Andrews,et al.  Raman and Infrared Spectra of LiO2 in Oxygen Matrices , 1972 .

[31]  R. S. Nicholson,et al.  Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. , 1964 .