Oxygen Reduction and Oxygen Evolution Reactions in Non-Aqueous Electrolyte As Studies By Dems

Tuesday, May 13, 2014: 16:40
Floridian Ballroom L, Lobby Level (Hilton Orlando Bonnet Creek)
H. Baltruschat, A. E. A. A. E. S. Abd-El-Latif, C. Molls, M. Khodayari, P. Hegemann, and C. BondŁ (University of Bonn)
Secondary lithium-air batteries are promising candidates for a future energy storage system as they provide in theory high capacity; however, in practice they show bad cyclebility. The key step in discharging these batteries is the reduction of oxygen present in air. So far the oxygen reduction reaction (ORR) has been investigated thoroughly in aqueous media, but little research has been done in non-aqueous solvents.
Organic carbonates are unsuitable for the use in lithium-air batteries because they decompose upon charging [1]. Recently Scrosati [2] showed by XRD that tetraethylene glycol dimethyl ether (tetraglyme) is an appropriate electrolyte for Li-air battery whereas Bruce [3] using XRD and FTIR techniques demonstrated that, tetraglyme is not the best electrolyte because it decomposes in the first few cycles. On the other hand, Li2O2 has been reported as the major discharge product using dimethyl sulfoxide (DMSO) as an electrolyte [4].  
Since spectroscopic techniques are superior to diffraction methods in detecting charge/discharge products, mass spectrometry in combination with electrochemistry (DEMS) has been used in this study to determine the electrolyte stability, water content, the amount of O2 reduced and evolved in a variety of aprotic electrolytes such as ethers (tetraglyme) and sulfoxide (DMSO). O2 solubility in aqueous and different non-aqueous electrolyte and its dependence on the flow rate of the electrolyte has been studied.

Crucial is a knowledge of the O2 solubility in these electrolytes. We will present a new method for its determination using differential electrochemical mass spectrometry (DEMS) based on the convection and diffusion behaviour characteristices of the dual thin layer cell used for DEMS. [5]


[1] F. Mizuno, et al., Electrochemitry, 2010, 78, 403. [2] H Jung et al., Nat. Chem., 2012, 4, 579. [3] S. Freunberger, et al., Angew. Chem. Int. Ed., 2011, 50, 8609. [4] Z. Peng, et al., Science, 2012, 337, 563. [5] Fuhrmann, J.; Linke, A.; Langmach, H.; Baltruschat, H., Numerical calculation of the limiting current for a cylindrical thin layer flow cell Electrochimica Acta 2009, 55, 430-438.